Herbicide preparation, a process for producing it and an activating additive for application therewith

ABSTRACT

PCT No. PCT/DK94/00099 Sec. 371 Date Sep. 8, 1995 Sec. 102(e) Date Sep. 8, 1995 PCT Filed Mar. 8, 1994 PCT Pub. No. WO94/19941 PCT Pub. Date Sep. 15, 1994Stable, concentrated herbicide preparation comprising at least one herbicide with at least one amino group, at least one carboxylic acid group and at least one phosphor containing acid group suspended in finegrained form in a liquid phase, and at least 5% by weight of a dissolved electrolyte; a process for producing said herbicide preparation and an activating additive (adjuvant) for combination with said herbicide preparation. Preferred suspensions comprise the herbicides glyphosate and glufosinate and the electrolyte ammonium sulphate, acting synergistically. It has not hitherto been possible to incorporate high concentrations of synergistic electrolytes in liquid concentrates of said herbicides.

This application has been filed under 35 USC 371 as the national stageof PCT/DK94/00099, filed Mar. 8, 1994.

The present invention relates to concentrated herbicide preparationscomprising at least one herbicide being fine-grained and suspended in anaqueous electrolyte solution, said herbicide comprising at least oneprimary, secondary or tertiary amino group and at least one carboxylicacid group and at least one phosphor containing acid group, a processfor producing it and an activating, concentrated additive forapplication in combination with said herbicides.

BACKGROUND OF THE INVENTION

It is customary to produce herbicide preparations as suspensions inwater. But normally the content of electrolytes in the aqueous phase islow, since a high content of electrolytes in water has a tendency tolower the solubility of the additives being necessary to stabilize theherbicide suspension. Amongst these additives, the surfactants areparticularly important, said surfactants being necessary to ensure thewetting in connection with the grinding of the suspended herbicide, andbeing often desirable in connection with the intrusion of the herbicidesin the weeds. Often only a few surfactants are suitable to ensure, in anappropriately broad temperature interval from -10° C. to approximately50° C., that the suspension is effectively wetted and also flowssatisfactorily. Additionally the suspensions almost always containsoluble, viscosity regulating compounds, ensuring that the viscosity ina broad temperature interval does not fall below a certain low value inorder to avoid precipitation of the suspended herbicide. A too highcontent of electrolytes in the aqueous phase might lead to thegelatination or precipitation of the viscosity regulating compounds. Thesurfactants as well as the viscosity regulating compounds and eventuallya certain amount of a dissolved glycol component can ensure, that thesuspension after freezing and subsequent unfreezing thaws out again as aflowable, not gritty suspension.

DESCRIPTION OF PRIOR ART

In published european patent application EP 388.239 A1 pesticidesuspensions are described, in which a certain amount of electrolytes isdesirable. The suspension of finely ground pesticides in a concentrationfrom 10-70% by weight in aqueous, structured systems of surfactants isdescribed. The following pesticides are mentioned explicitly:ethofumesate, phenmedipham, dazomet, mancozeb, methylene bisthiocyanate,amitraz and triforine. None of these pesticides contains both an acidand an amino group. The wording "structured systems of surfactants" isintended to mean aqueous systems, in which the surfactants formmesophases comprising structures larger than conventional sphericalmicelles and mutually interacting to form thixotropy in the aqueousmedium. The structure comprises multilayers of spherulites or lamellaedispersed or emulsified as rods or discs in an outer aqueous phase, thesize being normally 0.5-20 μm. In the 14 examples of the application thenot surface active electrolytes are present in an amount of 1.2-6.4% byweight of the total composition. It is a characteristic feature of thissystem, that the surfactant and the electrolyte must be adapted to eachother as regards composition and amount to obtain the desired, stablestructure.

Hungarian patent HU 200076 discloses, how the sedimentation tendency ofaqueous suspensions may be avoided by addition of electrolytes to thesuspensions. According to the patent lumps of surfactant will be formedwhen an electrolyte is added, causing the liquid to be turbid as thestabilisation takes place. It is not clearly evident from the patentwhether the stabilisation is caused by crystallisation of surfactant onthe surface of the suspended pesticide or by crystallisation ofsurfactant as a new phase (compare EP 388.239), or by theviscoelasticity caused by the precipitation. The improved stability isevaluated by centrifugation through indication of the not sedimentedpart. Only one of the samples (table 7) is subjected to normal long termstorage. The preferred electrolyte is diammonium hydrogen phosphate.According to the patent 5-10% diammonium hydrogen phosphate providesoptimal effect. It is not surprising that addition of electrolyteincreases the stability of an aqueous suspension, the viscosity normallybeing increased and frequently causing the suspension to gelatinate. Itis contrarily surprising, that the patent does not indicate theviscosity of the evaluated suspensions. All the examples compriseglycol, frequently about 10%. This addition counteracts the salting-outcaused by the electrolyte.

The adjustment of the viscosity of a suspension by changing an eventualcontent of electrolyte, surfactant and glycol being well-known, thistechnic, however, is almost never practiced at the final adjustment ofviscosity, because the effect is very dependent of temperature anddifficult to reproduce. Centrifugal tests are notoriously of norelevance for the long term stability of suspensions. HU 200076 does notdisclose that the amount of emulsifier necessary for sufficient wettingof the suspended pesticide may be reduced when an electrolyte is added.Similarly it is not disclosed in HU 200076, that the surfactant or theviscosity regulating polysaccharide may be omitted following theaddition of an electrolyte. There is a certain overlap between theintervals of added electrolyte in HU 200076 and in the presentinvention, but the optimal amount of electrolyte in the presentinvention is above the most effective in HU 200076. The describedpesticides are atrazine, isoproturon, bensultap, fluomethuron, lindane,thiophanat-methyl and elementary sulfur. None of these pesticidescomprises a carboxylic acid group or a phosphor containing acid group.

It is well known that ammonium sulphate acts synergistically on thebiological effect of glyphosate and glufosinate. For instance the patentliterature contains many examples of combinations of glyphosate andanmonium sulphate, and in practice the farmer usually adds supplementaryammonium sulphate when diluting the glyphosate for use.

Danish patent application no. 2348/88 describe liquid, aqueous solutionsof glyphosate with ethoxylated monoamines as surfactants. Thepossibility of dissolving additional ammonium sulphate exists, but thiswill lead to a lowering of the dissolvable quantity of glyphosate.Therefore, the maximum amount of glyphosate in a solution containing 280g/l ammonium sulphate is approximately 120 g/l.

UK patent application GB 2.233.229 A describes a similar system, theethoxylated monoamines being replaced by ethoxylated diamines. Thetypical, aqueous solutions contain 200 g/l ammonium sulphate and 75 g/lof glyphosate as its isopropylammonium salt.

UK patent application GB 2.245.170 A claims solutions of glyphosatecontaining ethoxylated phosphate esters as surfactants. In the examples,where ammonium sulphate has been added supplementary to the formulationin amounts of 200-300 g/l, the glyphosate constitutes 75 g/lcorresponding to 100 g/l of the isopropylammonium salt.

In European patent application EP 441.764 A1 is mentioned, thatalkoxylated, quaternary ammonium compounds especiallycoethoxylated-propoxylated quaternary ammonium compounds, isenvironmentally more acceptable and less skin and eye irritating thanethoxylated fatty amines. It is stated, that aqueous solutions ofglyphosate in combinations with said surfactants also can containammonium sulphate, but no examples with such formulations are given. Onthe other hand two solid compositions containing ammonium sulphate aredescribed.

In European patent application EP 498.785 A1 glyphosate formulations arementioned, which contain esters of sorbitol and fatty acids assurfactants in combination with another surfactant. It is mentioned,that these formulations whether aqueous solutions or solid, finelydistributed formulations may also contain ammonium sulphate or otherinorganic ammonium salts. The system, however, seems to be best suitedfor solid formulations.

European patent application EP 498.145 A1 describes solid compositionscontaining glyphosate as free acid or salt, an inorganic ammonium salt(preferably ammonium sulphate) and alkylglycoside or alkylpolyglycosideas surfactant.

European patent application EP 448.538 A1 describes combinations ofglyphosate and oxyfluorfen in solid formulations, additionallycontaining ammonium sulphate and other inorganic compounds.

International patent application WO 92/12637 deals with solid,preferably extruded or granulated formulations containing glyphosate incombination with alkaline compounds. A reaction takes place between theglyphosate and the alkaline compound either during the productionprocess or during the subsequent mixing with the diluent water tototally or partly neutralize the glyphosate as salt whereby it dissolveseasier and more quickly. The formulations shown besides comprisesurfactants and frequently ammonium sulphate.

In danish patent application no. 6490/89 solid formulations ofglyphosate in acid form containing a saturated C₁₆₋₁₈ -fatty alcohol,being ethoxylated with approximately 25 moles ethyleneoxide aredescribed. The formulations may additionally contain supplementaryammonium sulphate.

In german Offenlegungsschrift DE 3.926.800 A1 waterdispersablegranulates are mentioned, containing a herbicide (anyhow preferablyglufosinate) and 10-90% by weight of various anionic wetting agents.Examples of formulations with various amounts of ammonium sulphate areshown.

European patent application 243.872 A1 discloses pesticide preparations,comprising inter alia glyphosate dispersed in an oil containing, liquidphase. The addition to the formulations of ammonium sulphate is notmentioned.

French patent application 2.661.315 discloses the suspension ofglyphosate and derivatives thereof in an organic solvent. The organicsolvent might be water miscible, and it is mentioned that up to 50% ofthe solvent may be replaced by water. Furthermore the composition maycomprise ammonium sulphate, which is characterized as an adjuvant. Theform of the ammonium sulphate of the composition is not apparent fromthe description, but in the 5 examples of the application, the ammoniumsulphate together with the glyphosate compound seems to be totallysuspended or dissolved only to a limited extent in the liquid phase.

International patent application WO 92/21686 describes the production oftrimethylsulfonium salt of glyphosate for instance by the reaction ofglyphosate trimethylsulfonium hydrogen sulphate with an alkalinecompound like ammonia. The application does not mention herbicidalsuspensions in relation to the present invention. No description isfound, neither in the patent description nor in the examples, ofsignificant amounts of glyphosate being at any time suspended in anelectrolyte solution and certainly not in a stable form. The principlesof the present invention for formulating glyphosate, seem never to havebeen considered.

Many of the examples shown demonstrate the desirability of combining theherbicides glyphosate or glufosinate with ammonium sulphate and selectedsurfactants in one and the same formulation. Advantageously theformulation is as concentrated as possible.

As far as liquid, dissolved formulations are concerned, the ammoniumsulphate has a salting-out effect on the dissolved salts of glyphosateand glufosinate, as well as on the dissolved surfactants, and an upperlimit exists of the concentration of the solution dependent on theactual surfactant. Environmental requirements on the detergents, forinstance as to biodegradability, poor toxicity towards fishes and lowskin and eye irritation may reduce still further the number of relevantwetting agents. Besides, the various surfactants differ significantly intheir promotion of the biological effect of glyphosate and glufosinate.

Therefore, the trend in recent developments is towards solid, finelydispersed and non-dusty formulations. Although the solubility ofammonium sulphate in water is big, the speed of dissolution of ordinary,commercial, crystalline ammonium sulphate in water in practice is hardlyacceptable. Consequently, the crystalline ammonium sulphate frequentlyneeds to be grinded before being mixed with glyphosate or glufosinate orpreferably a salt thereof, the selected surfactant(s) and additive(s)being subsequently added. Amongst the additives adhesives, absorbingfillers or anticaking agents should be mentioned, which are necessary toobtain a finely dispersed, non-caking and easily flowing, solidformulation of adequate storage stability. For these processes anexpensive formulation equipment is necessary.

Despite the availability of these new types of highly sofisticated solidformulations, for example micro granulates or finely extruded materials,many users prefer to have liquid formulations. One of the reasons is theeasier measuring-out of how much of the composition to use, when theformulation is a liquid one.

Besides suppliers of spraying equipment are developing new types ofequipment, in which the automatic mixing with the diluent water takesplace immediately before spraying, said method being advantageous ofseveral reasons. For instance, all the farmer has to do is to fill thewater tank with water and place the concentrated pesticide preparationin the spraying equipment, the desired dilution automatically being madewhen driving. In such spraying systems the dosage of liquid formulationswill be easier than that of solid formulations.

SUMMARY OF THE INVENTION

The present invention is based on the surprising fact, that a stablesuspension can be attained by grinding a powdered herbicide with atleast one amino group, at least one carboxylic acid group and at leastone phosphor containing acid group in a bead mill in a higlyconcentrated solution of an electrolyte, which is not a surfactant perse, even if no surfactant is present.

In order to explain in greater detail the reasons for the above factbeing surprising, a number of requirements normally to be met whenproducing a stable suspension concentrate of a herbicide in a liquidphase--a so-called "flowable"--are listed below.

1) The herbicide must be very poorly soluble in the actual liquid, forinstance water, because when soluble to a certain extent in the liquid,the dissolved part of the herbicide, by cooling of the liquid, willprecipitate, mainly on the biggest of the fine, solid particles presentin the preparation, leading to crystal growth. When reheated mainly thesmallest crystals of herbicide will dissolve and so on. At constantlyfluctuating temperatures, which is normally the case in practice, thismeans a continuous crystal growth and an increased sedimentationtendency. This will normally give rise to serious storage problems.

2) It is necessary to add a surfactant to ensure optimal wetting of thesuspended particles of herbicide in the liquid. If the wetting isunsufficient, the suspension will become thick and consequentlyimpossible to grind in wet condition in a bead mill.

3) It is necessary to add a viscosity regulating agent in order tostabilize the final two-phased preparation.

4) It is necessary to add dissolved additives, which ensure that theproduct after drastic cooling and possibly freezing again thaws into astable and homogenous form without forming gritty lumps. This can beobtained by adding electrostatically acting dispersion agents, polymers(acting sterically hindering) and glycol compounds (lowering thefreezing point of the liquid). Frequently a combination of theseadditives is used..

Herbicides with at least one primary, secondary and/or tertiary aminogroup, at least one carboxylic acid group and at least one phosphorcontaining acid group normally have a relatively high solubility inwater: about 0.1% corresponding to 1000 ppm or more, preferably at least0.4% corresponding to 4000 ppm; by way of example the solubility ofglyphosate is approximately 1% by weight in pure water at 20° C.

By addition of an electrolyte during suspension in an aqueous phasecrystal growth of suspended herbicide is prevented, in fact a saltingout of the herbicide takes place. However, as mentioned above, a highcontent of electrolyte prevents the usual addition of additivesmentioned under items 2, 3 and 4 above, apart from the freezing pointlowering glycol compounds, said additives being normally regarded asabsolutely necessary for forming stable herbicide suspensions.

According to the invention, the wet grinding of a compound, which isalmost insoluble in the liquid phase, seems to take place withoutserious viscosity problems, even if no surfactant is added. This is veryuntypical. The reason could be, that the herbicide molecule contains anamino group as well as two acid groups. This explanation is madeprobable by the fact, that the surfactants being most difficult to saltout in electrolyte solutions, are those containing both negatively andpositively charged hydrophilic groups.

The fact, that the grinding can take place without viscosity problems,even when no surfactant is added, is probably an essential condition forrealising the invention. Even if a surfactant were added, the saltingout from the electrolyte of the compound would generally be soextensive, that the wetting effect of the insignificant amount stilldissolved in the water phase would be too small to influencesignificantly on the grinding. The surfactant, however, is stilldesirable. As mentioned above said surfactant is necessary to ensure theoptimum, biological effect of the formulation, and it might contributeto the stabilization of the final formulation, i.e. ensure that theformulation remains homogenous and does not separate. Apparently thefinely grinded, suspended herbicide and the added, finely distributedsurfactant mutually interact to produce a mixture of an advantageouspseudoplastic or thixotropic character. Accordingly, it is possible toproduce stable formulations comprising as the sole components water withdissolved electrolyte, suspended glyphosate and surfactant. It is evenpossible to produce stable suspensions using no surfactants at all.

When a surfactant is included in the suspension the surfactant mainlyappears to be uniformly distributed on the finely grinded herbicideparticles. This fact might contribute further to the stabilization ofcompositions, inter alia the coating causes the density differencesbetween the suspended and the liquid phase to be reduced.

There is some overlap regarding type of formulation and possiblecomponents between the present invention and French patent application2.661.315. It is therefore relevant to explain the differences betweenthe two systems.

In the French application the liquid phase mainly comprises an organicsolvent, while the present invention particularly uses water, whicheconomically and usually environmentally is the most advantageoussolvent. But that difference is not the decisive one. The fact that theelectrolyte according to the present invention is not suspended in theliquid phase, but normally totally dissolved in it, is far moreimportant. It leads to the following advantages:

a) The grinding of the ammonium sulphate is avoided (it is difficult todescribe this advantage, but the ammonium sulphate is so hard anddifficult to grind, and these difficulties can really only be understoodthrough practical experience in the laboratory). After all it seemscorrect to conclude, that even if the ammonium sulphate is pregrinded indry condition, the final grinding on the bead mill gives rise to greatproblems regarding material tear, low production speed and risk ofproduction stop.

b) An adjustment of the density of the grinded herbicide and the densityof the electrolyte solution in order to minimize the difference ispossible, whereby the separation tendency in the suspension becomes verylow. By coating the surf actant on the suspended herbicide furthervariations can be obtained. In French application 2.661.315, theherbicide as well as the electrolyte has to be suspended in the liquidphase, and there is accordingly no such possibility of adjusting thedensity of the liquid phase or of coating the suspended particles withthe surfactants.

c) By dissolving the electrolyte in a liquid phase a desirable loweringof the solubility of the suspended herbicide is obtained. Hereby agreater long term stability is obtained, because the risk of crystalgrowth is reduced (a generally accepted fact regarding suspensionpreparations).

d) In suspension preparations the amount of suspended solid material ina liquid phase must be below a certain upper limit. Normally thepractical limit is about 500 g/l suspension. In glyphosate preparationscontaining ammonium sulphate the desired content of ammonium sulphate aswell as that of glyphosate is high, and this is not possible to obtainif both compounds are to be suspended when the ammonium sulphate isdissolved in the water phase and the glyphosate only is dispersedherein, it is possible to increase the amounts of ammonium sulphate aswell as glyphosate.

Consequently the present invention differs from the description and the5 examples in French application 2.661.315 by having at least 5% byweight of electrolyte dissolved in the liquid, continuous phase. Example5 of the present application shows differences between the two systemsand clarifies the advantages of having the electrolyte dissolved in theliquid phase.

The herbicide preparations being stable means, that the suspendedherbicide in concentrated form does not precipitate or separate intosolid lumps, which on shaking of the preparation in the commercialpacking can not be resuspended in the liquid. Moreover the herbicidepreparations must be able to stand storage in the commercial packing forat least 1% year under normal storage conditions. The preparations beingon concentrated form means, that the product is in a commercial packingand that a dilution must take place before use.

The invention accordingly relates to stable, concentrated herbicidepreparations comprising at least one herbicide in an amount of 5-58% byweight, said herbicide being fine-grained and suspended in a liquidaqueous phase, and said herbicide containing at least one primary,secondary or tertiary amino group, at least one carboxylic acid groupand at least one phosphor containing acid group, said herbicidepreparations being characterized by comprising at least 5% by weight ofan electrolyte, which is dissolved in the liquid, aqueous phase and,which is not a surfactant.

If nothing else is stated, the indication "% by weight" or "%" in thepresent application means % by weight of the total composition.

DESCRIPTION OF PREFERRED EMBODIMENTS

For economical reasons it is advantageous, that the suspensions are asconcentrated as possible. On the other hand the solubility properties ofthe electrolytes determines the minimum of the water content. The lowerlimit for the water content is low, because a part of the watertheoretically can be substituted by an organic, water miscible solvent,which is also able to dissolve the electrolyte. In the preferredsuspensions of the invention, the water content is max. 65%, preferablymax. 60%, especially max. 55%, particularly max. 50% and specially max.45%, compare claim 2; in the suspensions the water content is generallymin. 12%, preferably min. 15%, especially min. 20%, particularly min.25% and specially min. 30%, i.e. intervals of for instance 12-65%,preferably 15-60%, especially 20-55%, particularly 25-50% and specially30-45%.

The liquid, aqueous phase should be continuous regarding water, but cancontain water miscible, organic solvents. The amount of water in thecontinuous solvent phase will normally constitute at least 52%,preferably at least 55%, especially at least 60%, particularly at least67% and specially at least 75% calculated as % by weight of the totalamount of solvent in the liquid and continuous, aqueous phase (compareclaim 3). (Water is calculated as solvent).

Said suspended herbicides with at least one amino group, at least onecarboxylic acid group and at least one phosphor containing acid groupwill frequently be such, where the phosphor containing acid group isselected from amongst. phosphonic acids and phosphinic acids.

Specially preferred herbicides are glyphosate(N-(phosphonomethyl)-glycine), glufosinate (4-(hydroxy (methyl)phosphinoyl)-DL-homoalanine), bilanafos(4-hydroxy(methyl)phosphinoyl)-L-homoalanyl-L-alanyl-L-alanin) and/orglyphosine (N,N-bis(p-hosphonomethyl)glycine), compare claim 4.

The actual suspended herbicides of the invention are applicable as such,i.e. in their free, non-neutralized form, or they can be reacted withacid or base into completely or partly neutralized salts, compare claim5. Amongst the acidic salts, hydrochlorides and sulfuric acid saltsshould be mentioned. Salts formed by reaction with base are for instancealkanolamine salts, amine salts, sodium salts and potassium salts andespecially ammonium salts. Amongst the more special salts,trimethylsulfonium and trimethylsulfoxonium salts should be mentioned.

Preferably the suspended herbicide is present in its free,non-neutralized form or as a mixture of a salt and free, non-neutralizedform comprising max. 80%, preferably max. 70%, especially max. 60% andspecially max. 50% of the herbicide transformed into a salt or, as athird possibility, comprising min. 50%, preferably min. 60%, especiallymin. 70% and specially min. 80% of the herbicide transformed into a saltlike an ammonium salt or a metal salt (by "%" is meant mole percents).Since the herbicide contains two or more acid groups, the transformationinto salt is to be calculated for the most acidic acid group only, theother groups being not included in the calculation.

Specially preferred suspensions are those, in which the herbicides arein their free, non-neutralized form or completely or partly reacted withammonia into the respective ammonium salts, compare claim 6.

The amount of the suspended herbicide in the compositions of theinvention is preferably min. 10%, especially min. 14%, particularly min.18% and specially min. 21%; on the other hand the suspended herbicideconstitutes max. 51%, especially max. 44%, particularly max. 38% andspecially max. 33% so, i.e. intervals of for instance preferably 10-51%,especially 14-44%, particularly 18-38% and specially 21-33%, compareclaim 7.

The described herbicide suspensions are generally characterized by thefact that said herbicides, when dissolved in water (1 part concentrateto 99 parts of water, eventually to 499 parts of water) dissolvescompletely in the diluent water. The pH in a 1% solution in water ismin. 1, preferably min. 1.5, especially min. 2 and specially min. 2.5.The pH will normally be max. 7, preferably max. 6, especially max. 5 andspecially max. 4.4 so, i.e. intervals of pH of for instance 1-7,preferably 1.5-6, especially 2-5 and specially 2.5-4.4.

If desired, different herbicides in combination can be used in theherbicide suspensions of the invention.

The invention also relates to stable, activating additives (adjuvants)on concentrated form, said adjuvants being active when admixed withglyphosate- and/or glufosinate preparations for combatting weeds, andsaid additives comprising at least one surfactant in an amount of 4-58%by weight, said surfactant being emulsified, suspended and/or dissolvedin a liquid, aqueous phase; the composition of the adjuvant beingfurther characterized by comprising at least one undissolved,fine-grained, not biologically active viscosity regulating filler actingto prevent separation of the surfactant, said viscosity regulatingfiller comprised in an amount of min. 0.3% by weight, and said liquid,aqueous phase being characterized by comprising an electrolyte, which isdissolved in the liquid, aqueous phase and, which is not a surfactant,in an amount of min. 5%.

Such a stable, activating additive is in a way an intermediate for theproduction of a concentrated suspension of glyphosate and/or glufosinateaccording to the invention, since the herbicide suspension can beproduced from the additive simply by admixing finely grinded herbicide.

To produce the herbicidal solution/suspension for use, the farmer maymake use of the additive, too. He just has to mix it with a glyphosate-or a glufosinate preparation. The form of the herbicide is of minorimportance in this connection, for instance a finely grinded powder, asolid granulate, a solution in an appropriate solvent or even asuspension may be used.

The wording "electrolyte", whether used in connection with the herbicidepreparations or the additive according to the invention, is intended tomean a single salt or a single salt or a mixture of two or more salts.Generally the electrolyte per se can not be regarded as a herbicide.

The electropositively charged part of the electrolyte can be as wellorganic as inorganic, and the electronegatively charged part can be aswell organic as inorganic, but normally a salt is preferred, in whicheither the positively charged or the negatively charged part isinorganic; a completely inorganic electrolyte is especiallyadvantageous, compare claim 8.

Among the electrolytes with characteristic, electropositively chargedions amine salts, alkanol amine salts, trimethylsulfonium salts,trimethylsulfoxonium salts and metal salts with mono-, di- or trivalentmetal ions should be mentioned. Specially preferred electrolytes areselected from among ammonium salts, compare claim 9.

Among the electrolytes with characteristic, electronegatively chargedions carboxylic acid salts, di- and tricarboxylic acid salts,hydroxycarboxylic acid salts, sulfonic acid salts and phosphonic acidsalts should be mentioned. Specially preferred electrolytes are selectedfrom among sulphates, chlorides, phosphates, phosphites, nitrates,nitrites, rhodanides, sulfamates, sulfites, dithionites andthiosulphates, compare claim 10.

Partly acidic salts such as ammonium hydrogensulphate and ammoniumdihydrogenphosphite formed from not monovalent acid rests can be used aswell.

As specially preferred electrolytes ammonium sulphate, ammoniumchloride, ammonium hydrogenphosphate, ammonium nitrate, ammoniumrhodanide, ammonium sulfamate and ammonium thiosulphate should bementioned.

The amount of the dissolved electrolyte in the composition is preferablymin. 10%, more preferably min. 12,5%, especially min. 15, particularlymin. 18% and specially min. 21%. On the other hand the amount of thedissolved electrolyte is generally max. 60%, preferably max. 53%, morepreferably max. 49%, especially max. 46%, particularly max. 41% andspecially max. 36% so, i.e. intervals of for instance 5-60%, preferably10-53%, more preferably 12,5-49%, especially 15-46%, particularly 18-41%and specially 21-36%, compare claim 11.

Furthermore the composition may comprise limited amounts of undissolvedelectrolyte. But usually this undissolved electrolyte will beundesirable, because of stability and succeeding solubility problems. Acontent of undissolved electrolyte might result from a separation at lowtemperatures.

Under certain special conditions, however, it is desirable for thecomposition to comprise undissolved electrolyte (salt). This will be thecase, if the undissolved salt is coated and therefore can not dissolvebefore the composition is mixed with water before the spraying in thefield. Under such conditions crystal growth of the salt is prevented,and the extra content of coated and dispersed salt can enhance thebiological effect of the preparation.

The total amount of electrolyte in the composition is preferably atleast 18%, especially at least 21%, particularly at least 23% andspecially at least 25%.

The solubility of the selected electrolyte in water influences themaximum amount of the electrolyte in the composition. So the upper limitfor the amount of the electrolyte is generally max. 75%, preferably max.68%, especially max. 60%, particularly max. 54% and specially max. 48%by weight of the electrolyte solution.

Preferred herbicidal compositions are such, in which the selectedherbicide is glyphosate or glufosinate, and the selected electrolyte isammonium sulphate.

To ensure the optimum biological effect, as mentioned above, saidherbicide suspensions preferably also comprise at least one surfactantconstituting 1-50%, said surfactant being emulsified, suspended and/oreventually dissolved in the liquid, aqueous electrolyte solution. Theamount of the surfactants in the composition is preferably min. 3%,particularly min. 6% and specially min. 10%; on the other hand theamount of the surfactants preferably is max. 38%, especially max. 31%and specially max. 26%, i.e. intervals of for instance preferably 3-38%,especially 6-31% and specially 10-26%, compare claim 12.

Regarding the adjuvant according to the invention the amount of thesurfactants in the composition is preferably min. 7%, particularly min.11% and specially min. 14%; on the other hand the amount of thesurfactants preferably is max. 48%, particularly max. 40% and speciallymax. 35%, i.e. intervals of for instance preferably 7-48%, particularly10-40% and specially 14-35%.

The wording "surfactants" includes emulsifiers, as well as dispersingand wetting agents. A surfactant might be a polymer with a molecularweight of below approximately 15,000 Dalton with many hydrocarbyl-and/or hydrocarbylene groups, or it must always contain at least onehydrocarbyl- or hydrocarbylene group containing at least 8 carbon atoms,or a polymethylesiloxane with at least 8 silicium atoms. Besides thesurfactant must contain at least one hydrophilic group, for example apolyoxyethylene group, an amine group, a sulfonic acid group or aphopsphate ester group, but this is no exhaustive characterization of asurfactant. Surfactants comprise compounds described in sales brochuresrelating to emulsifiers, dispersing and wetting agents and in cataloguesand works of reference for such. As examples of works of referenceMcCutcheon's publications: "Detergent & Emulsifiers InternationalEdition" and "North American Edition", Glen Rock, N.J. 07452, USA are tobe mentioned.

In the present application, the following definitions apply: Hydrocarbyl(R--) designates a linear aliphatic or branched aliphatic alkyl-,alkenyl- or alkynylgroup, illustrated by ethyl (--CH₂ CH₃), ethenyl(--CH═CH₂) or ethynyl (--C≡CH). Hydrocarbylene (--R--) designates alinear aliphatic or branched aliphatic alkylene, alkenylene- oralkynylene group, illustrated by ethylene (--CH₂ CH₂ --), ethenylene(--CH═CH--) or ethynylene (--C≡C--).

The surfactants may be of non-ionic, anionic, cationic or amphotericnature. Amines or quaternary compounds being additionally ethoxylated,are always regarded as cationic in this description.

The herbicide suspension and the adjuvant according to the invention maycomprise a mixture of different surfactants, for instance a mixture oftwo non-ionic surfactants or a mixture of a non-ionic and a ionicsurfactant.

The non-ionic surfactants may be selected from among such which areethoxylated, propoxylated or co-ethoxylated/propoxylated surfactants.The hydrophobic part of the non-ionic surfactants may be selected fromthe group consisting of mono-, di- or tristyrylphenol, naphtol, mono-,di- or tristyrylnaphtol, dicyclohexylphenol, mono-, di- ortristyryl-dicyclohexylphenol, phenylphenol, mono-, di- ortristyryl-phenylphenol, benzylphenol, mono-, di- ortristyryl-benzylphenol, formaldehyde condensed phenol or formaldehydecondensed naphtol, in which the above mentioned hydrophobic parts may besubstituted with one, two, three or four C₁₋₁₅ -alkyl groups, or thehydrophobic part may be selected from mono-, di-, tri- or tetra-C₁₋₁₈-alkylphenol or mono-, di-, tri- or tetra-C₁₋₁₈ -alkylnaphtol or C₈₋₃₀-hydrocarbylalcohol, C8-30 hydrocarbylcarboxylic acid, C₈₋₃₀-hydrocarbylene-di-carboxylic acid and abeetinic acid (rosin acid).Other corresponding non-ionic surfactants being methylated in theterminal OH-group of the polyalkoxylene groups or in which said OH-groupis linked to a new hydrocarbyl-group, preferably with the samecomposition as already mentioned, may be used, too.

From among the other types of non-ionic surfactants block-polymers(copolymerisates) of ethylene oxide and styren and of ethylene oxide(ethylene glycol) and propylene oxide (propylene glycol) should bementioned, whose molecular weight is in the interval from 1000 toapproximately 15,000 Dalton, preferably from 1500 to approximately12,000 Dalton and specially from 1,800 to approximately 10,000 Dalton.

Other preferred non-ionic surfactants are the ethoxylated, propoxylatedor co-ethoxylated/propoxylated vegetable oils as for example ricinusoil; fatty acid esters of polyalcohol as for example sorbitol, in itselfan emulsifier, which can be alkoxylated further (ethoxylated,propoxylated or co-ethoxylated/propoxylated); monoglycerides,diglycerides and polyalcoholates of natural fatty acids, which can beesterified further with C₁₋₄ -monocarboxylic acid (e.g. acetic acid),C₁₋₁₀ -dicarboxylic acid (e.g. adipic acid) and C₁₋₆ -hydroxycarboxylicacid (e.g. lactic acid), and which can be alkoxylated further. Amongother nonionic wetting agents of relevance N-C₄₋₁₆ -alkylpyrrolidone,speciallyN-C₈₋₁₆ -alkylpyrrolidone, hydrocarbylcarboxylic amide andalkoxylated variants hereof; alkoxylated hydrocarbylmercaptane,alkoxylated thiophenol and alkoxylated thionaphtol should be mentioned.

Specially preferred non-ionic surfactants are alkylglycosides,alkylpolyglycosides, alkoxylatedalkylglycosides, alkoxylatedalkylpolyglycosides, alkoxylated saccharides, alkoxylatedpolysaccharides, alkoxylated acetylene diols containing a symmetricallysubstituted triple bond and ethoxylated polymethylsiloxanes, compareclaim 13.

The anionic surfactants may be selected from the groups comprisingphosphate esters of for instance alkoxylated styrylphenols, alkylphenolsand hydrocarbylalcohols; substituted and unsubstituted sulfonic acids;esters and halfesters of sulfosuccinic acid; monosulphate esters ofC₈₋₂₀ -hydrocarbylalcohol and styrylalcohol derivatives; naphtalenesulfonic acid derivatives; sulfonated vegetable oils and sulfonatedmono- and diesters of natural fatty acids and sulfonated fatty acids;C₈₋₃₀ -hydrocarbylcarboxylic acid; C₈₋₃₀ -hydrocarbylene-dicarboxylicacids illustrated by C₄₋₁₆ -alkylsubstituted succinic acid;polycarboxylic acids; taurides and sarkosides and sulfamido carbonicacids. Additional types of anionic surfactants are (the corresponding)derivatives of polymethylsiloxanes.

The cationic surfactants may be selected from the group comprising C₈₋₃₀-hydrocarbylamine and C₈₋₃₀ -hydrocarbyl-di- and triamine beingalkoxylated with min. 1 preferably min. 2, especially min. 5 andspecially min. 8 oxyethylene and/or oxypropylene groups; quaternaryamines with min. one C₈₋₃₀ -hydrocarbyl and/or hydrocarbylene group andtheir alkoxylated derivatives; and amine modified polymethylsiloxanes.

The amphoteric surfactants are characterized by comprising at least oneC₈₋₃₀ -hydrocarbyl or at least one C₈₋₃₀ -hydrocarbylene group andalways at least one amino group and further one anionic group. Theanionic group may preferably be selected from among carboxylic acid,sulfonic acid and phosphonic acid.

Surfactants with ionic groups may be used in their free, unreacted form,but will often be totally or partly reacted to salt. The compositionshould not at the same time comprise significant amounts of an anionicas well as a cationic surfactant, and the surfactants are generallyselected accordingly.

Concerning those surfactants, for which it is possible to calculate aHLB-value (HLB=Hydrofil-Lipofil-Balance), this HLB-value shouldpreferably not be too low. The HLB-value should be min. 3, preferablymin. 4, especially min. 5, particularly min. 6 and specially min. 7.

Even though the presence of a surfactant in the herbicide suspension ofthe invention is desirable for biological reasons, a suspensioncomprising no surfactant has commercial interest, because of thepossibility of adding separately the surfactant. at the admixing stageof said suspension with the diluent water. The surfactant might beformulated as an activating additive according to the invention. Theadvantage of this system is, that the farmer may adjust individually thesurfactant to the amount of herbicide.

It is possible to adjust the suspension to enable most surfactants tophysically enter it. The suspended herbicide helps preventing thesurfactant from separating out. The surfactant is generally present inthe suspension in a non-structured form. Therefore in most of thedescribed herbicide suspensions comprising a surfactant, the surfactantwill separate as an independent, liquid phase or as solid particles incase the suspended herbicide and solid additives, if any, are removedfrom the suspensions.

The present invention does not relate to the final dilutions made at theuser level. The invention relates to concentrates only, being herbicidepreparations or activating additives, which according to the inventionare formulated in a new and more advantageous way. Since dilutions ofuse, made from the concentrates to a certain extent are well known,because they can be obtained by separate addition of ammonium sulphateto known products, and they are known to posses a particularlysatisfying biological effect, it seems redundant to proove the effect ofthe described compositions. There might be differences in the pH-valuesof the dilutions. For instance the pH-value of the herbicidepreparations according to the invention is frequently low, because theglyphosate is preferably used in its non-neutralized form, but this factis known to be of no biological importance. Reference is made in thisconnection to Danish patent application 6490/89, specially dealing withglyphosate on non-neutralized form.

In order to further stabilize the compositions physically to ensure thesmallest extent possible of sedimentation of the herbicide duringstorage i.e. to ensure a minor extent only of separation of a clearliquid, it might be desirable for the suspensions to comprise aviscosity regulating compound. At low electrolyte concentration, theviscosity regulating compound might be a water soluble polymer beingcompletely or partly dissolved (swelled) in the water phase. Among thepossible types thereof polycarboxylates, polyvinylpyrrolidones andcopolymerisates thereof should be mentioned. Another type of watersoluble polymers is polysaccharides, such as xanthane gum.

The optimal content of electrolyte is normally so high, thatwatersoluble polymers, f.ex. xanthane gum (Kelzan S or Rohdopol B 23),if present in the suspension, would either gelatinate or separate onundissolved form.

According to claim 14 the compositions of the invention preferablycomprise viscosity regulating compounds selected from among finelydistributed fillers tending not to sediment in the electrolyte solution,and of a particle size of max. 5 μm, preferably max. 1 μm, especiallymax. 0.3 μm and specially max. 0.1 μm. The fillers might be naturallyoccurring and synthetic clays and silicates, for instance naturalsilicium dioxides such as diatomaceous earth; calcium- andmagnesiumsilicates, such as talcs; magnesium aluminium silicates, suchas attapulgites and vermiculites; aluminium silicates, such askaolinites, montmorillonites and mica; synthetic, hydrated siliciumoxide units and synthetic calcium or aluminium silicates; natural resinsand synthetic resins such as coumarone resins, polyvinyl chloride andstyrene polymers and copolymers; solid fertilizers such assuperphosphates. Inorganic fillers are preferred. Especially preferredare fillers such as attapulgit, bentonite and hectorite and organicderivatives thereof such as Benton™. In addition to the separationsuppressing effect an added filler frequently improves the grinding ofthe pesticide, particularly if the grinding is performed in the wetstate in a bead mill.

As regards herbicide suspensions of the invention the appropriate amountof the viscosity regulating filler generally is max. 18%, preferablymax. 11%, especially max. 7% and specially max. 4%; on the other handthe amount of the viscosity regulating filler should be min.approximately 0.1%, preferably min. 0.3%,. especially min. 0.5% andspecially min. 0.9%, i.e. intervals of for instance 0.1-18%, preferably0.3-11%, especially 0.5-7% and specially 0.9-4%, compare claim 15.

As regards the additive of the invention an appropiate amount of theviscosity regulating filler is max. 22%, preferably max. 18%, especiallymax. 14% and specially max. 10%; on the other hand the amount of theviscosity regulating filler should be min. 1%, especially min. 2% andspecially min. 3.6%, i.e. intervals of for instance 0.3-22%, preferably1-18%, especially 2-14% and specially 3.6-10%.

Whether a herbicide suspension or an activating additive of theinvention, when this composition comprises a viscosity regulating, watersoluble polymer, an appropriate amount thereof is 0.01-3%, preferably0.03-2%, especially 0.1-1.5% and specially 0.3-1%.

Amongst other viscosity regulating compounds having the additionaleffect of improving the cold stability and acting hygroscopiccally, thecompositions of the invention might comprise glycols, polyglycols,glycerine, polymerizedglycerine, glycolethers, polyglycolethers,polyalcohols and urea, all having a solubility in water at 20° C. of atleast 1% by weight. Examples of glycols are ethylene glycol, propyleneglycol and hexylene glycol. Examples of polyglycols are diethyleneglycol, triethylene glycol, polyethylene glycol, dipropylene glycol,tripropylene glycol and water soluble polypropylene glycols. Examples ofpolyglycolethers are diethylene glycol butylether, dipropylene glycolmethylether, dipropylene glycol butylether and tripropylene glycolbutylether. Examples of polyalcohols are sorbitol, trimethylolpropan andpentaerythritol. None of the polyglycols, glycolethers and polyalcoholsshould be surfactants. The components of the abovementioned group ofcompounds may be present in the composition in an amount of max. 25%,preferably max. 18%, especially max. 11% and specially max. 7%; on theother hand they should be present in an amount of approximately min.0.1%, preferably min. 0.7%, especially min. 1.4% and specially min.2.4%, i.e. intervals of 0.1-25%, preferably 0.7-18%, especially 1.4-11%and specially 2.4-7%.

The compositions of the invention might comprise hygroscopic compounds,possibly also acting to stabilize pH and selected from the groupconsisting of hydroxycarboxylic acids, di- and tricarboxylic acids andtheir hydroxy acids, said acids being present as free acids and having asolubility in water at 20° C. of at least 1% by weight. Examples of suchacids are lactic acid, oxalic acid, succinic acid, tartaric and citricacid. The amount of these acids in the composition may be approximately0.1-22%, preferably 0.4-16%, especially 1-11% and specially 2-7%.

Another group of compounds being able to promote the biological effect,for instance by improving the intrusion of the herbicides into thetreated plants, is the group of oily compounds. The composition of theinvention accordingly may comprise oils or oily compounds, thesolubilities thereof in water at 20° C. being below 1% by weight, theboiling points thereof at atmospheric pressure being min. 200° C.,preferably min. 230° C. and specially min. 260° C., and which areselected from the group comprising carbonhydride oils, triglycerideoils, preferably synthetic ester oils with one or two estergroups permolecule, hydrocarbylcarboxylic acids, hydroxyhydrocarbylcarboxylicacids, hydrocarbylalcohols, hydrocarbylenedialcohols, water insolublepolypropylene glycols and silicone oils. An example of a carbonhydrideoil is mineral oil. Examples of triglyceride oils are vegetable oils andmarine oils. Examples of carboxylic acids are oleic acid, lauric acidand pelargonic acid. An example of hydroxyhydrocarbylcarboxylic acid isricinoleic acid. Examples of hydrocarbylalcohols are n-decanol andisodecanol.

The number of carbon atoms in the ester oils with one or two estergroups per molecule is 8-72, preferably 10-60, especially 12-46 andspecially 14-44. Those ester oils which do not additionally compriseether groups are preferred. Examples thereof are methyl oleate, butyloleate, 2-ethylhexyl stearate, propylene glycol dioleate anddi-(2-ethylhexyl) sebacate.

The components of this group of oils or oily compounds are present inthe composition of the invention in an amount of max. 24%, preferablymax. 17%, especially max. 11% and specially max. 7%; on the other handthey should be present in an amount of min. 0.1%, preferably min. 0.7%,especially min. 1.4% and specially min. 2.4%, i.e. intervals of forinstance 0.1-2.4%, preferably 0.7-17%, especially 1.4-11% and specially2.4-7%.

The herbicide suspension according to the invention is usually producedby a process, where the herbicide and eventually other components aregrinded and admixed with the other components. The same principleapplies for the production of the additive according to the invention. Asubsequent adjustment may be necessary.

The grinding and possibly the admixing may preferably take place in abead mill, for instance at a temperature in the interval of 0°-50° C. Inorder to maintain the temperature in this interval cooling of the beadmill with water or ice water will usually be necessary. If thesurfactant has a higher melting point, it might be desirable to raisethe temperature of the mill to 50°-60° C. for a period. This may beeffected by temporarily stopping the cooling water. The surfactant isadded in the molten state at the higher temperature, and finely grindedfiller, if any, is usually added before the cooling with cooling wateris resumed.

To avoid foaming it is frequently advantageous to postpone the additionof surfactant to after the grinding.

The average particle size of the herbicide in the compositions of theinvention, as for instance determined using a Malvern Particle Sizer ofthe type 3600 E using low effect laser light diffraction technic or anequivalent method, must be max. 72 μm, specifically max. 48 μm,preferably max. 29 μm, especially max. 19 μm, particularly max. 13 μmand specially max. 8 μm; on the other hand the average particle sizemust be min. 0.2 μm, specifically min. 0.3 μm, preferably min. 0.5 μm,especially min. 1 μm, particularly min. 2 μm and specially min. 3.5 μm,i.e. intervals of for instance 0.2-72 μm, specifically 0.3-48 μm,preferably 0.5-29 μm, especially 1-19 μm, particularly 2-13 μm andspecially 3.5-8 μm, compare claim 16.

The invention also relates to a special process for producing theherbicide suspension according to the invention, said process beingcharacterized by comprising the following steps, compare claim 18:Firstly a highly concentrated solution of the herbicide as salt in wateris formed. To this solution either acid or base is added to precipitatethe herbicide in completely or partly free non-salt form; theelectrolyte solution is formed from the rest of the salt initiallyhaving formed salt with the herbicide, and the added amount of acid orbase, and the precipitation is controlled so as to produce particles ofa sufficiently small size to reduce or preferably leave out thesubsequent grinding on the bead mill. In order for the herbicideparticles to become of a sufficiently small size, the addition of acidor base preferably takes place as controlled as possible, which normallymeans, that the addition takes place during simultaneous cooling and/orvigorous stirring and/or through a suitable injector system.

Specially preferred herbicide suspensions comprise glyphosate suspendedin ammonium sulphate, said suspensions being produced by adding sulfuricacid to solutions of the ammonium salt of glyphosate or adding ammoniato a solution of the sulfuric acid salt of glyphosate, preferably whilecooling and continuously stirring.

Or the suspensions may be produced by wet grinding (on a beadmill) ofthe herbicide in the electrolyte solution. Other additives may be addedeither before or after the grinding.

The viscosity of preferred compositions of the invention at 25° C. ismax. 7900 cp (mPa x s), preferably max. 4900 cP, especially max. 2900 cPand specially max. 2000 cP. On the other hand the viscosity should bemin. 70 cP, preferably min. 150 cP, especially min. 275 cP and speciallymin. 440 cP, i.e. intervals of for instance 70-7900 cP, preferably150-4900 cP, especially 275-2900 cP and specially 440-2000 cP, asmeasured with a Brookfield viscosimeter equipped with a spindel of thetype RV.

As packaging material for the suspensions, certain polymers may be used,which are soluble in water and insoluble in the electrolyte solutions,in which the herbicide is suspended. Among such polymerspolyvinylalcohol and methyl cellulose should be mentioned.

In the preferred dilutions of use of the herbicide preparations and theactivating additives, the amount of the concentrate in the finaldilution of use is 0.2-10%, preferably 0.4-6%, especially 0.7-4% andspecially 1-3% by weight of the dilution of use, corresponding to adosage per hectar of 0.3-15 1/ha, preferably 0.6-9 l/ha, especially 1-6l/ha and specially 1.5-4.5 l/ha.

The amount of the herbicide, for instance glyphosate or glufosinate,constitutes 0.2-4 kg/ha, preferably 0.3-3 kg/ha, especially 0.5-2.2kg/ha and specially 0.8-1.5 kg/ha, calculated on an active ingredientbasis.

The examples below illustrate the production of stable suspensionsaccording to the invention.

Example 1

Experiments 1-5 (see table A) demonstrates the suspension of glyphosatein free, non-neutralized form in an aqueous solution of ammoniumsulphate. Calculated on the aqueous solution the amount of ammoniumsulphate is 40% in all 5 experiments corresponding to a saturation inwater at approximately 0° C. In all of the examples, ethoxylated fattyamines are used as surfactants.

For the manufacture of the compositions 1 and 2 the Genamine (theethoxylated fatty amine) was initially dissolved in a part of the water,following which the pH was adjusted with concentrated sulfuric acid topH=3.5. The rest of the water was then added and subsequently theammonium sulphate was stirred in, leading to the precipitation of thechief of the Genamine. The mixture was transferred as quantitatively aspossible to a mini-mill with a volume of maximally 50 ml from thecompany Eiger Engineering Ltd., Warrington, Cheshire, England, beingfilled with 1-2 mm zirkonium oxide pearls. The mill was startedimmediately at its highest speed, and the addition of glyphosate wasstarted. After 5 minuttes all glyphosate was added. The grinding wascontinued for further approximately 10 minuttes. Attagel was added, andthe grinding was continued for maximally 5 minuttes.

For the manufacture of the compositions 3, 4 and 5, the ammoniumsulphate was initially dissolved in the total amount of water, followingwhich the concentrated sulfuric acid was added, and the solution wastransferred to the mini-mill. The mill was started at its highest speed,following which the addition of glyphosate was started. After 5 minuttesall glyphosate was added. The grinding was continued for furtherapproximately 10 minuttes. Genamin was added immediately followed byAttagel, and the grinding was continued for approximately 5 minutes.

In table A, the various components and the amounts thereof are listed.

Samples of the above compositions were stored in 100 ml glass bottleswith screw caps for 1 to approximately 4 weeks before the beginning ofthe accelerated testing. It was initially evaluated, whether the samplehad separated a clear aqueous phase, and whether the surfactant hadseparated out on its own. The results of all evaluations are listed intable A. Subsequently the sample was shaken. The viscosity was visuallyevaluated, and the average particle size of the grinded glyphosateparticles was estimated microscopically at 256 x. (It is very difficultto use a particle sizer for so many samples, because the samples must bemeasured in concentrated salt solutions possibly further saturated withglyphosate, in order to ensure, that the samples are not dissolved inthe water. It is also important that the concentrated salt solution doesnot contain undissolved impurities, which might disturb themeasurements). It was also estimated, whether the added surfactants hadseparated out as oily drops. If so, the estimated size of the drops wasnoted. If no oily drops could be observed, a "n.d." (not detected) isstated in the table. It should be noted, that any microscopic airbubblespresent may give rise to a false positive result.

After the evaluation a part of the content of the 100 ml bottles wastransferred to 60 ml glass bottles to fill all bottles approximatelyhalf. The 60 ml bottles were stored for 14 days at 55° C. The 100 mlbottles were stored as follows:

72 hours: 55° C.

24 hours: Ambient temperature

24 hours: -18° C.

24 hours: Ambient temperature

96 hours: 55° C.

24 hours: Ambient temperature

24 hours: -18° C.

24 hours: Ambient temperature

24 hours: 55° C.

Totally 14 times 24 hours.

After this testing period both groups of samples were cooled to ambienttemperature and evaluated as mentioned above. Supplementary the speed ofdissolution was determined as follows: 1 ml suspension was pipetted offand placed in a 150 ml beaker containing 100 ml deionized water. Themixture was stirred on a magnetic stirrer of moderate speed using a 4 cmmagnet so as to produce an approximately 1 cm deep vortex in the diluentwater, and the period of time until no more undissolved glyphosate couldbe observed was measured in seconds. All observations are listed intable A.

Evaluation and conclusion

The results of the evaluation are estimated subjectively. The valueindicated, however, may constitute a sufficient basis for estimatingwhether the suspensions during storage undergo undesirable changes of astability destroying nature.

The most difficult evaluation is that of the viscosity. It is evaluated,whether the samples show pseudoplastic properties, but the presence ofsuch properties can not be estimated visually for all samples. Thepseudoplastic properties, being desirable in suspension preparations inorder to avoid sticking sediments, are therefore only indicated forthose samples, in which they are unmistakable. In the tables thefollowing definitions are used:

Sufficiently=sufficiently flowing, i.e. an appropriate viscosity.

Easily=easily flowing. The sample has an appropriately low viscosity,but sedimentation might take place during long time storage.

Very easily=very easily flowing. Probably a too low viscosity, but nosticking sedimentation was observed.

Slightly viscous=the viscosity is not very far removed from the upperlimit of what is acceptable, and it should not be increased.

Somewhat viscous=unacceptable, high viscosity.

Viscous=much too high viscosity.

Pseudoplastic=an appropriate viscosity of the desired pseudoplasticnature.

Clearly pseudo=pseudoplastic, perhaps too viscous when plastic thesample is at rest.

Upp. cl. phase=upper clear phase

All samples in table A shows acceptable storage properties. Someuncertainty exists as to the results of the measurements of the speedsof dissolution, but the level must be characterized as satisfactory.

                                      TABLE A                                     __________________________________________________________________________    Experiment no.                                                                          1     2    3     4    5                                             __________________________________________________________________________    Components                                                                              Composition in %                                                    Deionized water                                                                         41.6  41.1 41.0  41.0 40.8                                          Ammonium sulphate                                                                       27.8  27.4 27.4  27.4 27.2                                          Glyphosate, 98%                                                                         20.8  20.6 20.6  20.6 20.4                                          Genamin T 150 (1)                                                                       6.9   6.8                                                           Genamin O 80 (2)     6.8                                                      Genamin C 100 (3)          6.8                                                Genamin C 020 (4)               6.8                                           Sulfuric acid, 98%                                                                      app. 1.5                                                                            app. 1.4                                                                           2.1   2.1  2.7                                           Attagel (5)                                                                             1.4   2.7  2.1   2.1  2.1                                           Total weight (g)                                                                        144   146  146   146  147                                           Density (g/ml)                                                                          1.30  1.29 1.28  1.28 1.25                                          Glyphosate (g/l)                                                                        270   266  264   264  255                                           Ammonium sulphate                                                                       361   353  351   351  340                                           (g/l)                                                                                   Evaluation before storage                                           Appearance                                                                              15% upp.                                                                            10% upp.                                                                           10% upp.                                                                            10% upp.                                                                           10% upp.                                                cl. phase                                                                           cl. phase                                                                          cl. phase                                                                           cl. phase                                                                          cl. phase                                     Viscosity pseudo-                                                                             slightly                                                                           slightly                                                                            pseudo-                                                                            pseudo-                                                 plastic                                                                             viscous                                                                            viscous                                                                             plastic                                                                            plastic                                       Particle size (μm)                                                                   app. 10                                                                             app. 10                                                                            5-10  app. 10                                                                            5-10                                          Oil drops (μm)                                                                       n.d.  n.d. n.d.  n.d. n.d.                                                    Evaluation after storage at various temperatures                    Appearance                                                                              30% upp.                                                                            20% upp.                                                                           15% upp.                                                                            25% upp.                                                                           25% upp.                                                cl. phase                                                                           cl. phase                                                                          cl. phase                                                                           cl. phase                                                                          cl. phase                                     Viscosity easily                                                                              suffici-                                                                           suffici-                                                                            easily                                                                             easily                                                        ently                                                                              ently                                                    Particle size (μm)                                                                   app. 10                                                                             10-15                                                                              app. 10                                                                             10-15                                                                              5-10                                          Oil drops (μm)                                                                       n.d.  n.d. n.d.  n.d. n.d.                                          Speed of dissol. (s)                                                                    4     6    3     3    2                                                       Evaluation after storage 14 days at 55° C.                   Appearance                                                                              15% upp.                                                                            5% upp.                                                                            10% upp.                                                                            10% inner                                                                          15% upp.                                                cl. phase                                                                           cl. phase                                                                          cl. phase                                                                           cl. phase                                                                          cl. phase                                     Viscosity pseudo-                                                                             slightly                                                                           pseudo-                                                                             pseudo-                                                                            pseudo-                                                 plastic                                                                             viscous                                                                            plastic                                                                             plastic                                                                            plastic                                       Particle size (μm)                                                                   app. 10                                                                             10-15                                                                              app. 10                                                                             10-15                                                                              app. 10                                       Oil drops (μm)                                                                       n.d.  n.d. n.d.  n.d. n.d.                                          Speed of dissol. (s)                                                                    3     4    4     2    7                                             __________________________________________________________________________

Example 2

Experiments 6-10, 11-15, 16-20, 21-25 and 26-29 in the tables B, C, D,E, and F describe glyphosate compositions comprising various surfactantsin varying amounts. The ratio glyphosate/surfactant is about 2/1corresponding to the usual ratio in most commercial products. The amountof finely distributed fillers varies from 0 to 2% by weight. In all ofthe experiments the amount of the electrolyte ammonium sulphate isvarying from app. 20 to 27 by weight. The grinding is performed in amini-mill as described for the samples 3-5 in table A, the sulfuric acidaddition, however, being omitted.

The melting points of Marlipal 1618/25 and Radiasurf 7417 are about 55°C. Therefore, the mixtures in experiments 26 and 27 were heated to50°-55° C. during the addition of Marlipal and Radiasurf.

Evaluation and conclusion

No tendency to separate sticking sediments was observed in any of theexamples. After shaking the flowing properties seem acceptable. Asubsequent re-evaluation of the experiments revealed that air bubbles bymistake under the microscope had been regarded as oil drops. No separateoil layers were seen. The speeds of dissolution in water are generallyvery good.

No relevant comparison with other suspension preparations can be made,because of the aqueous suspension preparations, dissolving in thediluent water, being an unusual type of formulation.

                                      TABLE B                                     __________________________________________________________________________    Experiment no.                                                                            6    7    8    9    10                                            __________________________________________________________________________    Component                                                                                 Composition in %                                                  Deionized water                                                                           40.5 40.5 40.5 40.5 40.5                                          Ammonium sulphate                                                                         27.0 27.0 27.0 27.0 27.0                                          Glyphosate, 98%                                                                           20.3 20.3 20.3 20.3 20.3                                          Ethoquad C/25 (6)                                                                         10.2                                                              Emcol CC 55 (7)  10.2                                                         Ampholyt SKKP-70 (8)  10.2                                                    Synperonic NP-10 (9)       10.2                                               Tween 20 (10)                   10.2                                          Attagel (5) 2.0  2.0  2.0  2.0  2.0                                           Total weight (g)                                                                          148  148  148  148  148                                           Density (g/ml)                                                                            1.28 1.27 1.27 1.27 1.27                                          Glyphosate (g/l)                                                                          260  258  258  258  258                                           Ammonium sulphate                                                                         346  343  343  343  343                                           (g/l)                                                                                     Evaluation before storage                                         Appearance  no se-                                                                             no se-                                                                             15% lower                                                                          15% lower                                                                          10% lower                                                 paration                                                                           paration                                                                           cl. phase                                                                          cl. phase                                                                          cl. phase                                     Viscosity   slightly                                                                           easily                                                                             slightly                                                                           slightly                                                                           slightly                                                  viscous   viscous                                                                            viscous                                                                            viscous                                       Particle size (μm)                                                                     app. 10                                                                            app. 10                                                                            10-15                                                                              10-15                                                                              10                                            Oil drops (μm)                                                                         n.d. n.d. n.d. n.d. 25-100                                                    Evaluation after storage at various temperatures                  Appearance  20% upp.                                                                           30% upp.                                                                           no se-                                                                             20% upp.                                                                           15% upp.                                                  cl. phase                                                                          cl. phase                                                                          paration                                                                           cl. phase                                                                          cl. phase                                     Viscosity   easily                                                                             easily                                                                             passende                                                                           passende                                                                           passende                                                            viscous                                                                            viscous                                                                            viscous                                       Particle size (μm)                                                                     app. 5                                                                             app. 10                                                                            app. 10                                                                            app. 10                                                                            10-15                                         Oil drops (μm)                                                                         n.d. n.d. n.d. n.d. n.d.                                          Speed of dissol. (s)                                                                      2    2    3    3    2                                                         Evaluation after storage 14 days at 55° C.                 Appearance  10% upp.                                                                           25% upp.                                                                           no se-                                                                             no se-                                                                             10% upp.                                                  cl. phase                                                                          cl. phase                                                                          paration                                                                           paration                                                                           cl. phase                                     Viscosity   pseudo-                                                                            easily                                                                             pseudo-                                                                            slightly                                                                           pseudo-                                                   plastic   plastic                                                                            viscous                                                                            plastic                                       Particle size (μm)                                                                     5-10 5-10 app. 10                                                                            10-15                                                                              10-15                                         Oil drops (μm)                                                                         n.d. n.d. n.d. n.d. n.d.                                          Speed of dissol. (s)                                                                      4    1    3    7    2                                             __________________________________________________________________________

                                      TABLE C                                     __________________________________________________________________________    Experiment no.                                                                          11    12   13    14   15                                            __________________________________________________________________________    Component                                                                               Composition in %                                                    Deionized water                                                                         40.5  40.5 40.5  40.5 40.5                                          Ammonium sulphate                                                                       27.0  27.0 27.0  27.0 27.0                                          Glyphosate, 98%                                                                         20.3  20.3 20.3  20.3 20.3                                          Plantaren 225 (11)                                                                      10.2                                                                Plantaren 600 CS (12)                                                                         10.2                                                          Berol 02 (13)        10.2                                                     Berol 922 (14)             10.2                                               Pleuriol PE6400 (15)            10.2                                          Attagel (5)                                                                             2.0   2.0  2.0   2.0  2.0                                           Total weight (g)                                                                        148   148  148   148  148                                           Density (g/ml)                                                                          1.28  1.28 1.28  1.27 1.28                                          Glyphosate (g/l)                                                                        260   260  260   258  260                                           Amm. sulphate (g/l)                                                                     346   346  346   343  346                                                     Evaluation before storage                                           Appearance                                                                              Foaming                                                                             15% lower                                                                          no se-                                                                              no se-                                                                             15% upp.                                                10% lower                                                                           cl. phase                                                                          paration                                                                            paration                                                                           cl. phase                                               cl. phase                                                           Viscosity pseudo-                                                                             suffici-                                                                           clearly                                                                             pseudo-                                                                            pseudo-                                                 plastic                                                                             ently                                                                              pseudo-                                                                             plastic                                                                            plastic                                                            plastic                                                  Particle size (μm)                                                                   10-15 app. 10                                                                            app. 10                                                                             app. 15                                                                            app. 15                                       Oil drops (μm)                                                                       n.d.  n.d. <25   25-100                                                                             >100                                                    Evaluation after storage at various temperatures                    Appearance                                                                              5% inner                                                                            20% upp.                                                                           10% upp.                                                                            15% upp.                                                                           30% upp.                                                cl. phase                                                                           cl. phase                                                                          cl. phase                                                                           cl. phase                                                                          cl. phase                                     Viscosity suffici-                                                                            suffici-                                                                           suffici-                                                                            easily                                                                             easily                                                  ently ently                                                                              ently                                                    Particle size (μm)                                                                   10-15 10-15                                                                              5-10  app. 15                                                                            app. 15                                       Oil drops (μm)                                                                       n.d.  n.d. n.d.  n.d. n.d.                                          Speed of dissol. (s)                                                                    46    12   2     6    2                                                       Evaluation after storage 14 days at 55° C.                   Appearance                                                                              no se-                                                                              20% upp.                                                                           no se-                                                                              no se-                                                                             no se-                                                  paration                                                                            cl. phase                                                                          paration                                                                            paration                                                                           paration                                      Viscosity pseudo-                                                                             suffici-                                                                           viscous*                                                                            pseudo-                                                                            pseudo-                                                 plastic                                                                             ently      plastic                                                                            plastic                                       Particle size (μm)                                                                   10-15 10-15                                                                              5-10  app. 15                                                                            app. 15                                       Oil drops (μm)                                                                       n.d.  n.d. n.d.  n.d. n.d.                                          Speed of dissol. (s)                                                                    25    14   23    6    4                                             __________________________________________________________________________     *screw cap leaky, crystals from the liquid observed.                     

                                      TABLE D                                     __________________________________________________________________________    Experiment no.                                                                            16   17   18   19   20                                            __________________________________________________________________________    Component                                                                                 Composition in %                                                  Deionized water                                                                           40.5 40.8 40.8 40.5 40.5                                          Ammonium sulphate                                                                         27.0 27.2 27.2 27.0 27.0                                          Glyphosate, 98%                                                                           20.3 20.4 20.4 20.3 20.3                                          Tween 85 (16)                                                                             10.2                                                              Ethoquad C/25 (6)                                                                              10.2                                                         Arkopon T hockonc. (17)                                                                             10.2                                                    Berol 987 (18)             10.2                                               Surfadon LP 300 (19)            10.2                                          Aerosil R 972 (20)                                                                             1.4                                                          Attagel (5) 2.0       1.4  2.0  2.0                                           Total weight (g)                                                                          148  147  147  148  148                                           Density (g/ml)                                                                            1.26 1.26 1.28 1.27 1.26                                          Glyphosate (g/l)                                                                          256  257  261  258  256                                           Amm. sulphate (g/l)                                                                       340  343  348  343  340                                                     Evaluation before storage                                           Appearance  no se-                                                                             no se-                                                                             10% lower                                                                          no se-                                                                             no se-                                                    paration                                                                           paration                                                                           cl. phase                                                                          paration                                                                           paration                                      Viscosity   slightly                                                                           pseudo-                                                                            pseudo-                                                                            pseudo-                                                                            pseudo-                                                   viscous                                                                            plastic                                                                            plastic                                                                            plastic                                                                            plastic                                       Particle size (μm)                                                                     app. 10                                                                            10-15                                                                              app. 10                                                                            app. 10                                                                            app. 10                                       Oil drops (μm)                                                                         25-100                                                                             25-100                                                                             n.d. 25-100                                                                             <25                                                     Evaluation after storage at various temperatures                    Appearance  10% upp.                                                                           30% upp.                                                                           15% lower                                                                          no se-                                                                             no se-                                                    cl. phase                                                                          cl. phase                                                                          cl. phase                                                                          paration                                                                           paration                                      Viscosity   suffici-                                                                           pseudo-                                                                            pseudo-                                                                            pseudo-                                                                            pseudo-                                                   ently                                                                              plastic                                                                            plastic                                                                            plastic                                                                            plastic                                       Particle size (μm)                                                                     5-10 app. 10                                                                            app. 10                                                                            app. 10                                                                            app. 10                                       Oil drops (μm)                                                                         n.d. n.d. n.d. <25  n.d.                                          Speed of dissol. (s)                                                                      3    3    14   2    13                                                      Evaluation after storage 14 days at 55° C.                   Appearance  no se-                                                                             10% upp.                                                                           no se-                                                                             no se-                                                                             no se-                                                    paration                                                                           cl. phase                                                                          paration                                                                           paration                                                                           paration                                      Viscosity   slightly                                                                           pseudo-                                                                            slightly                                                                           pseudo-                                                                            some                                                      viscous                                                                            plastic                                                                            viscous                                                                            plastic                                                                            viscous                                       Particle size (μm)                                                                     5-10 10-15                                                                              5-10 10-15                                                                              5-10                                          Oil drops (μm)                                                                         n.d. n.d. n.d. 25-100                                                                             n.d.                                          Speed of dissol. (s)                                                                      5    2    19   4    20                                            __________________________________________________________________________

                                      TABLE E                                     __________________________________________________________________________    Experiment no.                                                                          21    22   23    24   25                                            __________________________________________________________________________    Component                                                                               Composition in %                                                    Deionized water                                                                         40.5  41.4 40.0  38.7 38.2                                          Ammonium sulphate                                                                       27.0  27.6 26.7  25.8 25.5                                          Glyphosate, 98%                                                                         20.3  20.7 20.0  19.4 19.1                                          Berol OX 45-11 (21)                                                                     10.2  10.3 13.3  16.1 15.9                                          Attagel (5)                                                                             2.0                   1.3                                           Total weight (g)                                                                        148   145  150   155  157                                           Density (g/ml)                                                                          1.26  1.26 1.26  1.25 1.25                                          Glyphosate (g/l)                                                                        256   261  252   243  239                                           Ammonium sulphate                                                                       340   348  337   323  319                                           (g/l)                                                                                   Evaluation before storage                                           Appearance                                                                              no se-                                                                              15% lower                                                                          15% lower                                                                           15% lower                                                                          10% lower                                               paration                                                                            cl. phase                                                                          cl. phase                                                                           cl. phase                                                                          cl. phase                                     Viscosity pseudo-                                                                             easily                                                                             easily                                                                              easily                                                                             slightly                                                plastic               viscous                                       Particle size (μm)                                                                   app. 15                                                                             10-15                                                                              app. 15                                                                             10-15                                                                              app. 10                                       Oil drops (μm)                                                                       <25   25-100                                                                             <25   25-100                                                                             25-100                                                  Evaluation after storage at various temperatures                    Appearance                                                                              5% upp.                                                                             35% upp.                                                                           30% inner                                                                           20% lower                                                                          5% inner                                                cl. phase                                                                           cl. phase                                                                          cl. phase                                                                           cl. phase                                                                          cl. phase                                     Viscosity clearly                                                                             very ea-                                                                           easily                                                                              suffici-                                                                           pseudo-                                                 pseudo-                                                                             sily       ently                                                                              plastic                                                 plastic                                                             Particle size (μm)                                                                   10-15 10-15                                                                              10-15 10-15                                                                              app. 10                                       Oil drops (μm)                                                                       <25   n.d. n.d.  n.d. n.d.                                          Speed of dissol. (s)                                                                    3     2    2     2    3                                                       Evaluation after storage 14 days at 55° C.                   Appearance                                                                              no se-                                                                              30% upp.                                                                           15% inner                                                                           15% lower                                                                          10% lower                                               paration                                                                            cl. phase                                                                          cl. phase                                                                           cl. phase                                                                          cl. phase                                     Viscosity clearly                                                                             very ea-                                                                           easily                                                                              suffici-                                                                           pseudo-                                                 pseudo-                                                                             sily       ently                                                                              plastic                                                 plastic                                                             Particle size (μm)                                                                   10-15 10-15                                                                              app. 15                                                                             10-15                                                                              10-15                                         Oil drops (μm)                                                                       <25   n.d. 25-100                                                                              n.d. 25-100                                        Speed of dissol. (s)                                                                    10    1    1     2    3                                             __________________________________________________________________________

                                      TABLE F                                     __________________________________________________________________________    Experiment no.                                                                          26    27   28    29   30                                            __________________________________________________________________________    Component                                                                               Composition in %                                                    Deionized water                                                                         40.8  40.5 40.9  47.2 40.5                                          Ammonium sulphate                                                                       27.2  27.0 27.3  20.3 27.0                                          Glyphosate, 98%                                                                         20.4  20.3 20.5  20.3 20.3                                          Marlipal 1618/25 (22)                                                                   10.2                                                                Radiasurf 7417 (23)                                                                           10.2                                                          Berol OX 45-11 (21)  10.3  10.2                                               Berol 533 (24)                  10.2                                          Aerosil R 972 (20)   1.0                                                      Attagel (5)                                                                             1.4   2.0        2.0  2.1                                           Total weight (g)                                                                        147   148  146.5 148  148                                           Density (g/ml)                                                                          1.27  1.28 1.26  1.22 1.26                                          Glyphosate (g/l)                                                                        345   346  258   248  256                                           Ammonium sulphate                                                                       259   260  344   248  340                                           (g/l)                                                                                   Evaluation before storage                                           Appearance                                                                              no se-                                                                              no se-                                                                             no se-                                                                              no se-                                                                             no se-                                                  paration                                                                            paration                                                                           paration                                                                            paration                                                                           paration                                      Viscosity slightly                                                                            slightly                                                                           pseudo-                                                                             pseudo-                                                                            pseudo-                                                 viscous                                                                             viscous                                                                            plastic                                                                             plastic                                                                            plastic                                       Particle size (μm)                                                                   app. 15                                                                             app. 15                                                                            app. 10                                                                             app. 15                                                                            app. 15                                       Oil drops (μm)                                                                       n.d.  25-100                                                                             25-100                                                                              25-100                                                                             >25                                                     Evaluation after storage at various temperatures                    Appearance                                                                              10% upp.                                                                            15% upp.                                                                           30% upp.                                                                            30% upp.                                                                           15% upp.                                                cl. phase                                                                           cl. phase                                                                          cl. phase                                                                           cl. phase                                                                          cl. phase                                     Viscosity clearly                                                                             pseudo-                                                                            pseudo-                                                                             pseudo-                                                                            suffici-                                                pseudo-                                                                             plastic                                                                            plastic                                                                             plastic                                                                            ently                                                   plastic                                                             Particle size (μm)                                                                   10-15 app. 10                                                                            app. 10                                                                             10-15                                                                              app. 10                                       Oil drops (μun)                                                                      n.d.  n.d. 25-100                                                                              n.d. n.d.                                          Speed of dissol. (s)                                                                    2     2    2     2    3                                                       Evaluation after storage 14 days at 55° C.                   Appearance                                                                              no se-                                                                              no se-                                                                             no se-                                                                              20% upp.                                                                           no se-                                                  paration                                                                            paration                                                                           paration                                                                            cl. phase                                                                          paration                                      Viscosity slightly                                                                            pseudo-                                                                            pseudo-                                                                             easily                                                                             viscous*                                                viscous                                                                             plastic                                                                            plastic                                                  Particle size (μm)                                                                   10-15 app. 10                                                                            app. 10                                                                             app. 15                                                                            app. 10                                       Oil drops (μm)                                                                       n.d.  n.d. n.d.  n.d. n.d.                                          Speed of dissol. (s)                                                                    7     3    2     2    17                                            __________________________________________________________________________     *Screw cap leaky, crystals from the liquid observed.                     

Example 3

Experiments 31-35, 36-40, 41-45 and 46-49 in the tables G. H, I and Jrelate to various glyphosate compositions. Experiments 31-33 (table G)relate to compositions with ammonium salts different from ammoniumsulphate. Experiments 34 and 35 (table G) relates to compositionscomprising herbicide only suspended in an electrolyte solution.Experiments 36-40 (table H) show the use of potassium thiocyanate,sodium bromide and ammonium acetate as electrolyte. In the experiments36 and 37, one of the acid groups in glyphosate is transformed into thesodium salt. In experiment 38, a little amount only of glyphosate istransformed into the sodium salt. In experiments 39 and 40, one of theacid groups in glyphosate is transformed into its ammonium salt. Theexperiments 41-45 (table I) relate to compositions comprising viscosityregulating, hygroscopic compounds. These are glycerine, propyleneglycol, polyethylene glycol and lactic acid. Obviously the addition ofthese to the aqueous phase caused no tendency to separation ofundissolved electrolyte. Experiments 46 and 47 relate to compositionsfurther comprising oil. Experiment 48 and 49 relate to compositionscomprising herbicide suspended in an electrolyte solution and smallamounts of a viscosity regulating filler, but no surfactant.

The grinding is performed in a mini-mill as described above for thesamples 3-5 in table A, the sulfuric acid addition being omitted.

In experiment 40 the composition comprising Marlipal 1618/25 wastemporarily heated.

Evaluation and conclusion

After shaking, the flowing properties seem satisfactory. The speeds ofdissolution of the samples of experiments 34 and 35 comprising nosurfactant, are inferior to those of the other samples, but acceptableanyhow. Generally speaking the speeds of dissolution are very good.

In the experiments 46 and 47, the oils apparently do not disperse ontothe grinded glyphosate, unlike the surfactants. This conclusion is basedpartly on the microscopy and partly on the experiment 46, in which thesample, which had been stored at varying temperatures, at the end of theexperiment had separated two upper, clear phases. This was not observedin experiment 47. In both samples, the oil was uniformly re-distributedin the compositions after shaking.

All samples from these experiments are at least acceptable.

                                      TABLE G                                     __________________________________________________________________________    Experiment no.                                                                            31   32   33   34   35                                            __________________________________________________________________________    Component                                                                                 Composition in %                                                  Deionized water                                                                           27.4 34.0 40.5 36.9 33.1                                          Ammonium sulfamate                                                                        41.1 17.0                                                         Ammonium sulphate                                                                              17.0      24.6 22.1                                          Ammonium nitrate      27.0                                                    Glyphosate, 98%                                                                           20.5 20.4 20.3 38.5 44.8                                          Berol OX 45-11 (21)                                                                       10.3 10.2 10.2                                                    Attagel (5) 0.7  1.4  2.0                                                     Total weight (g)                                                                          146  147  148  130  145                                           Density (g/ml)                                                                            1.35 1.29 1.25 1.33 1.38                                          Glyphosate (g/l)                                                                          277  263  254  512  618                                           Electrolyte (g/l)                                                                         555  439  338  327  305                                                       Evaluation before storage                                         Appearance  10% lower                                                                          no se-                                                                             no se-                                                                             20% upp.                                                                           10% upp.                                                  cl. phase                                                                          paration                                                                           paration                                                                           cl. phase                                                                          cl. phase                                     Viscosity   easily                                                                             slightly                                                                           easily                                                                             passende                                                                           slightly                                                       viscous   viscous                                                                            viscous                                       Particle size (μm)                                                                     app. 15                                                                            10-15                                                                              10-15                                                                              20-25                                                                              app. 20                                       Oil drops (μm)                                                                         25-100                                                                             25-100                                                                             25-100                                                                             n.d. n.d.                                                      Evaluation after storage at various temperatures                  Appearance  25% lower                                                                          10% upp.                                                                           30% upp.                                                                           30% upp.                                                                           20% upp.                                                  cl. phase                                                                          cl. phase                                                                          cl. phase                                                                          cl. phase                                                                          cl. phase                                     Viscosity   easily                                                                             pseudo-                                                                            easily                                                                             passende                                                                           slightly                                                       plastic   viscous                                                                            viscous                                       Particle size (μm)                                                                     app. 15                                                                            10-15                                                                              10-15                                                                              25-30                                                                              app. 20                                       Oil drops (μm)                                                                         <25  n.d. n.d. n.d. n.d.                                          Speed of dissol. (s)                                                                      2    3    2    32   12                                                        Evaluation after storage 14 days at 55° C.                 Appearance  15% lower                                                                          no se-                                                                             30% upp.                                                                           30% upp.                                                                           15% upp.                                                  cl. phase                                                                          paration                                                                           cl. phase                                                                          cl. phase                                                                          cl. phase                                     Viscosity   easily                                                                             pseudo-                                                                            easily                                                                             easily                                                                             slightly                                                       plastic        viscous                                       Particle size (μm)                                                                     app. 15                                                                            10-15                                                                              app. 15                                                                            app. 25                                                                            app. 20                                       Oil drops (μm)                                                                         n.d. n.d. 25-100                                                                             n.d. n.d.                                          Speed of dissol. (s)                                                                      3    5    2    16   6                                             __________________________________________________________________________

                                      TABLE H                                     __________________________________________________________________________    Experiment no.                                                                            36   37   38   39   40                                            __________________________________________________________________________    Component                                                                                 Composition in %                                                  Deionized water                                                                           27.0 23.7 37.8 27.6 26.3                                          Kalium thiocyanate                                                                             42.1                                                         Ammonium sulfamate                                                                        40.5                39.5                                          Natrium bromide       29.7                                                    Ammonium acetate           33.8                                               Glyphosate, 98%       20.3                                                    Glyphosate Na-salt                                                                        20.3 23.0                                                         Glyphosate NH.sub.4 -salt  27.6 23.0                                          Berol OX 45-11 (21)                                                                       10.2 9.9  10.1 9.2                                                Marlipal 1618/25 (22)           9.9                                           NaOH, 28%             1.4                                                     Attagel (5) 2.0  1.3  0.7  1.8  1.3                                           Total weight (g)                                                                          148  152  148  163  152                                           Density (g/ml)                                                                            1.33 1.24 1.39 1.35 1.35                                          Glyphosate salt (g/l)                                                                     270  285  282  373  310                                           Electrolyte (g/l)                                                                         539  522  413  456  533                                                       Evaluation before storage                                         Appearance  10% lower                                                                          5% lower                                                                           10% inner                                                                          no se-                                                                             no se-                                                    cl. phase                                                                          cl. phase                                                                          cl. phase                                                                          paration                                                                           paration                                      Viscosity   pseudo-                                                                            suffici-                                                                           easily                                                                             pseudo-                                                                            clearly                                                   plastic                                                                            ently     plastic                                                                            pseuplas.                                     Particle size (μm)                                                                     app. 15                                                                            10-15                                                                              10-15                                                                              30-50                                                                              app. 15                                       Oil drops (μm)                                                                         n.d. <25  n.d. n.d. 25-100                                                    Evaluation after storage at various temperatures                  Appearance  10% lower                                                                          10% lower                                                                          25% upp.                                                                           no se-                                                                             10% lower                                                 cl. phase                                                                          cl. phase                                                                          cl. phase                                                                          paration                                                                           cl. phase                                     Viscosity   clearly                                                                            suffici-                                                                           easily                                                                             clearly                                                                            clearly                                                   pseuplas.                                                                          ently     pseuplas.                                                                          pseuplas.                                     Particle size (μm)                                                                     20-25                                                                              app. 15                                                                            10-15                                                                              app. 50                                                                            app. 20                                       Oil drops (μm)                                                                         n.d. n.d. n.d. n.d. n.d.                                          Speed of dissol. (s)                                                                      3    5    3    9    2                                                         Evaluation after storage 14 days at 55° C.                 Appearance  10% lower                                                                          10% lower                                                                          20% upp.                                                                           no se-                                                                             no se-                                                    cl. phase                                                                          cl. phase                                                                          cl. phase                                                                          paration                                                                           paration                                      Viscosity   clearly                                                                            suffici-                                                                           easily                                                                             clearly                                                                            clearly                                                   pseuplas.                                                                          ently     pseuplas.                                                                          pseuplas.                                     Particle size (μm)                                                                     15-20                                                                              10-15                                                                              app. 15                                                                            30-50                                                                              app. 15                                       Oil drops (μm)                                                                         n.d. n.d. n.d. <25  n.d.                                          Speed of dissol. (s)                                                                      7    8    5    21   5                                             __________________________________________________________________________

                                      TABLE I                                     __________________________________________________________________________    Experiment no.                                                                            41   42   43   44   45                                            __________________________________________________________________________    Component                                                                                 Composition in %                                                  Deionized water                                                                           38.0 38.0 13.6 38.0 22.1                                          Ammonium sulfamate    20.5      32.2                                          Ammonium sulphate                                                                         25.3 25.3      25.3                                               Glyphosate, 98%                                                                           19.0 19.0 20.6 19.0 25.0                                          Berol OX 45-11 (21)                                                                       9.5  9.5  10.3 9.5                                                Glycerine   6.3       34.3                                                    Propylene glycol                20.7                                          PEG E200 (27)    6.3                                                          Lactic acid                6.3                                                Attagel (5) 1.9  1.9  0.7  1.9                                                Total weight (g)                                                                          158  158  146  158  140                                           Density (g/ml)                                                                            1.27 1.25 1.30 1.27 1.34                                          Glyphosate (g/l)                                                                          241  238  268  241  335                                           Electrolyt (g/l)                                                                          321  316  267  321  431                                                       Evaluation before storage                                         Appearance  no se-                                                                             no se-                                                                             no se-                                                                             no se-                                                                             20% upp.                                                  paration                                                                           paration                                                                           paration                                                                           paration                                                                           cl. phase                                     Viscosity   pseudo-                                                                            pseudo-                                                                            pseudo-                                                                            clearly                                                                            easily                                                    plastic                                                                            plastic                                                                            plastic                                                                            pseudo-                                                                       plastic                                            Particle size (μm)                                                                     app. 15                                                                            app. 10                                                                            app. 15                                                                            app. 15                                                                            app. 10                                       Oil drops (μm)                                                                         25-100                                                                             >100 n.d. 25-100                                                                             n.d.                                                      Evaluation after storage at various temperatures                  Appearance  no se-                                                                             10% upp.                                                                           10% lower                                                                          5% upp.                                                                            35% upp.                                                  paration                                                                           cl. phase                                                                          cl. phase                                                                          cl. phase                                                                          cl. phase                                     Viscosity   pseudo-                                                                            pseudo-                                                                            pseudo-                                                                            clearly                                                                            easily                                                    plastic                                                                            plastic                                                                            plastic                                                                            pseudo-                                                                       plastic                                            Particle size (μm)                                                                     10-15                                                                              app. 10                                                                            app. 15                                                                            app. 15                                                                            app. 10                                       Oil drops (μm)                                                                         n.d. n.d. n.d. n.d. n.d.                                          Speed of dissol. (s)                                                                      2    2    4    2    3                                                         Evaluation after storage 14 days at 55° C.                 Appearance  no se-                                                                             no se-                                                                             no se-                                                                             no se-                                                                             25% upp.                                                  paration                                                                           paration                                                                           paration                                                                           paration                                                                           cl. phase                                     Viscosity   clearly                                                                            pseudo-                                                                            pseudo-                                                                            clearly                                                                            easily                                                    pseudo-                                                                            plastic                                                                            plastic                                                                            pseudo-                                                        plastic        plastic                                            Particle size (μm)                                                                     app. 15                                                                            5-10 app. 15                                                                            app. 15                                                                            app. 10                                       Oil drops (μm)                                                                         n.d. n.d. n.d. n.d. n.d.                                          Speed of dissol. (s)                                                                      8    2    5    2    3                                             __________________________________________________________________________

                  TABLE J                                                         ______________________________________                                        Experiment no.                                                                             46       47       48     49                                      ______________________________________                                        Component                                                                                Composition in %                                                   Deionized water                                                                            38.0     38.0     40.5   57.6                                    Ammonium sulphate                                                                          25.3     25.3     27.0   14.3                                    Glyphosate, 98%                                                                            19.0     19.0     30.5   25.2                                    Berol 02 (13)                                                                              6.3      6.3                                                     Hydropar 19 (25)                                                                           9.5                                                              Radia 7131 (26)       9.5                                                     Attagel      1.9      1.9      2.0    2.9                                     Total weight (g)                                                                           158      158      148    139                                     Density (g/ml)                                                                             1.22     1.21     1.34   1.22                                    Glyphosate (g/l)                                                                           232      230      409    174                                     Ammonium sulphate                                                                          309      306      362    307                                     (g/l)                                                                                    Evaluation before storage                                          Appearance   10% lower                                                                              15% lower                                                                              no se- 10% upp.                                             cl. phase                                                                              cl. phase                                                                              paration                                                                             cl. phase                               Viscosity    suffici- suffici- pseudo-                                                                              easily                                               ently    ently    plastic                                        Particle size (μm)                                                                      app. 20  app. 15  10-15  20-25                                   Oil drops (μm)                                                                          >100     25-100   n.d.   n.d.                                               Evaluation after storage at various temperatures                   Appearance   30% 2    30% lower                                                                              10% upp.                                                                             10% upp.                                             upp. cl. cl. phase                                                                              cl. phase                                                                            cl. phase                                            phases                                                           Viscosity    suffici- pseudo-  pseudo-                                                                              easily                                               ently    plastic  plastic                                        Particle size (μm)                                                                      app. 15  10-15    10-15  20-25                                   Oil drops (μm)                                                                          >100     >100     n.d.   n.d.                                    Speed of dissol. (s)                                                                       2        2        2      22                                                 Evaluation after storage 14 days at 55° C.                  Appearance   15% lower                                                                              20% lower                                                                              no se- no se-                                               cl. phase                                                                              cl. phase                                                                              paration                                                                             paration                                Viscosity    suffici- pseudo-  pseudo-                                                                              easily                                               ently    plastic  plastic                                        Particle size (μm)                                                                      app. 15  app. 15  10-15  20-25                                   Oil drops (μm)                                                                          >100     >100     n.d.   n.d.                                    Speed of dissol. (s)                                                                       4        5        2      4                                       ______________________________________                                    

Example 4

Experiments 50 and 51 in table K relate to compositions comprising nosuspended herbicide, but a surfactant and a viscosity regulating fillersuspended in an electrolyte solution.

Experiments 52-55 in table L relate to glufosinate suspended in anaqueous electrolyte solution. The electrolyte is either ammoniumsulphate or ammonium sulfamate. The samples of experiments 52-54 furthercomprise a surfactant. The sample of experiment 55, on the other hand,comprises only water, ammonium sulphate and glufosinate.

The samples were produced in a mini-mill as described above.

Evaluation and conclusion

Apparently, the glufosinate compositions are generally a little thin andtherefore has a tendency to separate a clear liquid. This might becompensated for by changing the ratio between suspended solids andliquid electrolyte solution.

The speeds of distribution and dissolution are very favourable. Theother physical properties appear completely satisfactory.

                  TABLE K                                                         ______________________________________                                        Experiment no.   50          51                                               ______________________________________                                        Component                                                                                    Composition in %                                               Deionized water  42.8        41.7                                             Ammonium sulphate                                                                              28.6        27.8                                             Moussex 904 SE (28)          0.7                                              Ethoquad C/25 (6)                                                                              25.0                                                         Berol OX 45-11 (21)          27.8                                             Attagel 40 (5)   3.6         2.0                                              Total weight (g) 140         144                                              Density (g/ml)   1.15        1.14                                             Glyphosate (g/l) --          --                                               Ammonium sulphate                                                                              329         317                                              (g/l)                                                                                        Evaluation before storage                                      Appearance       10% lower   10% lower                                                         cl. phase   cl. phase                                        Viscosity        suffici-    suffici-                                                          ently       ently                                            Particle size (μm)                                                                          --          --                                               Oil drops (μm)                                                                              >100        25-100                                                          Evaluation after storage at various                                           temperatures                                                   Appearance       30% lower   25% lower                                                         cl. phase   cl. phase                                        Viscosity        suffici-    suffici-                                                          ently       ently                                            Particle size (μm)                                                                          --          --                                               Oil drops (μm)                                                                              n.d.        n.d.                                                            Evaluation after storage 14 days                                              at 55° C.                                               Appearance       10% lower   5% lower                                                          cl. phase   cl. phase                                        Viscosity        suffici-    suffici-                                                          ently       ently                                            Particle size (μm)                                                                          --          --                                               Oil drops (μm)                                                                              n.d.        n.d.                                             ______________________________________                                    

                  TABLE L                                                         ______________________________________                                        Experiment no.                                                                             52       53       54     55                                      ______________________________________                                        Component                                                                                Composition in %                                                   Deionized water                                                                            41.0     27.2     42.9   40.0                                    Ammonium sulfamate    40.8                                                    Ammonium sulphate                                                                          27.3              28.6   26.7                                    Glufosinat, 97%                                                                            20.5     20.4     21.4   33.3                                    Berol OX 45-11 (21)                                                                        10.2     10.2                                                    Arkopon T hochkonc             7.1                                            (17)                                                                          Attagel      1.0      1.4                                                     Total weight (g)                                                                           146.5    147      140    120                                     Density (g/ml)                                                                             1.23     1.23     1.26   1.27                                    Glufosinat (g/l)                                                                           252      251      270    423                                     Electrolyte (g/l)                                                                          336      502      360    339                                                Evaluation before storage                                          Appearance   10% lower                                                                              20% lower                                                                              35% lower                                                                            30% lower                                            cl. phase                                                                              cl. phase                                                                              cl. phase                                                                            cl. phase                               Viscosity    suffici- easily   easily easily                                               ently                                                            Particle size (μm)                                                                      10-15    app. 15  app. 15                                                                              15-20                                   Oil drops (μm)                                                                          n.d      n.d.     >100   n.d.                                               Evaluation after storage at various temperatures                   Appearance   15% lower                                                                              25% lower                                                                              45% upp.                                                                             30% inner                                            cl. phase                                                                              cl. phase                                                                              cl. phase                                                                            cl. phase                               Viscosity    easily   easily   easily easily                                  Particle size (μm)                                                                      app. 10  app. 10  10-15  app. 15                                 Oil drops (μm)                                                                          n.d.     n.d.     n.d.   n.d.                                    Speed of dissol. (s)                                                                       4        6        3      18                                                 Evaluation after storage 14 days at 55° C.                  Appearance   15% lower                                                                              20% lower                                                                              45% upp.                                                                             30% inner                                            cl. phase                                                                              cl. phase                                                                              cl. phase                                                                            cl. phase                               Viscosity    suffici- easily   easily easily                                               ently                                                            Particle size (μm)                                                                      10-15    10-15    app. 10                                                                              15-20                                   Oil drops (μm)                                                                          n.d.     n.d.     n.d.   n.d.                                    Speed of dissol. (s)                                                                       4        3        6      3                                       ______________________________________                                    

Example 5

The purpose of the example is to illustrate the difference between thepresent invention and French application 2.661.315.

In the French application, the most hydrophilic solvent mixture and themixture comprising the most water, is the mixture in example 1,comprising 250 g water and 300 g propylene glycol per liter. Thismixture, therefore, is able to dissolve the most ammonium sulphate. 5%by weight of the weight of 1 liter product (1192 g) is 59.6 g. Inexperiment 56 (table M) this amount of ammonium sulphate is dissolved inthe actual amount of water (250 g) followed by addition of the citedamount of propylene glycol (300 g) (both per liter product). A fastprecipitation of ammonium sulphate is observed.

The actual surfactant of the French example 1, a derivative of anethoxylated fatty amine, is not commercially available, and issynthesized from ethylene oxide (extremely poisonous). Experiments 57and 58 are intended to show, that compounds being comparable to thissurfactant do not solubilize the ammonium sulphate. Consequently theamount of dissolved ammonium sulphate in example 1 in FR 2.663.315 cannot exceed 5% w/w. Genamin S 25 is the most ethoxylated of thecommercially available ethoxylated fatty amines. In experiment 57Genamin S 25 is admixed with propylene glycol, before the mixture isadded to the ammonium sulphate solution. PEG 400 is polyethylene glycolcomprising on an average 8 moles of ethylene glycol. Since this compounddoes not comprise any hydrophobic group, it is more hydrophilic thanethoxylated fatty amines, and therefore probably has a greater impact onthe solubility of ammonium sulphate. In experiment 58 PEG 400 is admixedwith the propylene glycol, before the mixture is added to the ammoniumsulphaate solution. Both example 57 and 58 show a precipitation ofammonium sulphate following the addition of the propylene glycolmixtures to the aqueous ammonium sulphate solutions.

Conclusion

None of the compositions in the examples of FR 2.661.315 comprises 5%w/w or more of dissolved ammonium sulphate.

                  TABLE M                                                         ______________________________________                                                      Experiment no.                                                                56      57       58                                             Component       Composition in g                                              ______________________________________                                        Deionized water 250.0     250.0    250.0                                      Ammonium sulphate                                                                             59.6      59.6     59.6                                       Propylene glycol                                                                              300.0     300.0    300.0                                      Genamin S 25 (29)         200.0                                               PEG 400                            200.0                                      Undissolved ammonium                                                                          Yes       Yes      Yes                                        sulphate at 25° C.                                                     ______________________________________                                    

Example 6

The product of experiment 59 in table N has been produced and grinded ona mini-mill in the same way as in experiments 6-30 in example 2.

The product of example 60 has been produced by initially dissolving theammonium sulphate in water (40% ammonium sulphate solution) followed byadmixture of propylene glycol, leading to a precipitation of ammoniumsulphate. The stirring on the mini-mill was started, and the glyphosatewas added in the usual way followed by admixture of Genapol OX-130.

The viscosity was measured at 20° C. by means of a BrookfieldRVF-viscosimeter (gear 20). The much higher viscosity in experiment 60,comprising only half as much ammonium sulphate as experiment 59, iscaused by the fact, that the ammonium sulphate in experiment 59 istotally dissolved in the liquid, aqueous phase, whereas the ammoniumsulphate in experiment 60 is predominantly dispersed in the 50% w/wpropylene glycol-/water phase.

At normal temperatures an ammonium sulphate solution comprisesapproximately 40% ammonium sulphate. In experiment 61 20 g ammoniumsulphate was dissolved in the water phase followed by addition ofpropylene glycol, causing a precipitation of ammonium sulphate. Another20 g ammonium sulphate was finely grinded in a blender with a view toadding it slowly during grinding before the addition of glyphosate,before the addition of Genapol and after the addition of Genapol,respectively.

In practice, the grinding showed up to be impossible, because thecrystals of ammonium sulphate were too hard to grind and stopped thefilter, keeping the pearls in the mill. Accordingly it was impossible togrind the ammonium sulphate in experiment 62, where no water was presentto dissolve part of the ammonium sulphate.

Experiments 61 and 62 show, that ammonium sulphate precipitated as finecrystals from an aqueous solution by addition of a water-miscible,organic solvent gives rise to no problems, whereas finely grindedcrystals of ammonium sulphate are difficult to grind further on abead-mill.

                  TABLE N                                                         ______________________________________                                                     Experiment no.                                                                59    60        61     62                                        Component      Composition in g                                               ______________________________________                                        Deionized water                                                                              60.0    30.0      30.0                                         Ammonium sulphate                                                                            40.0    20.0      40.0 40.0                                    Propylene glycol       30.0      30.0 60.0                                    Glyphosate, 98%                                                                              30.0    30.0      30.0 30.0                                    Genapol OX 130 (30)                                                                          20.0    20.0      20.0 20.0                                    Viscosity Brook-                                                                             1800    3100      --   --                                      field at 20° C.                                                                       mPaxs   mPaxs                                                  ______________________________________                                    

Example 7

A preferred composition of glyphosate in electrolyte solution comprisesthe following:

169.1 g glyphosate

225.4 g ammonium sulphate

338.2 g water

112.8 g Genapol OX-130 (30)

The above mentioned composition is produced as follows (using the methodof claim 18):

169.1 g glyphosate is dissolved in 266 g water and 80 g aqueous 25% w/wammonia solution together with 159,4 g ammonium sulphate in a beaker andis transferred to another container under vigorous stirring.

51.0 g sulfuric acid (96% w/w) is added over 10 minutes at approximately25° C. 112.8 g molten Genapol OX-130 is added with vigorous stirring,the stirring being continued for 5 minutes.

End pH: 3.5

Density: 1.17 g/ml (the mixture contains some air)

1.25 g/ml (after evacuation)

Particle size: 20-25 μm

Chemicals

1. Genamin™ T-150: Tallow fatty amine ethoxylated with 15 oxyethyleneunits (Hoechst).

2. Genamin™ O-080: Oleylamine ethoxylated with 8 oxyethylene units(Hoechst).

3. Genamin™ C-100: Fatty amine from coconut oil ethoxylated with 10oxyethylene units (Hoechst).

4. Genamin™ C-020: Fatty amine from coconut oil ethoxylated with 2oxyethylene units (Hoechst).

5. Attagel™ 40: Attapulgitclay, colloidal grades (Chemie-MineralienGmbH).

6. Ethoquad™ C25: (Coco)alkyl methylammonium chloride ethoxylated with15 oxyethylene units (Akzo).

7. Emcol™ CC 55: Alkoxylated quaternary ammonium salt (Witco).

8. Ampholyt SKKP-70: (Coco)alkyl-β-aminopropionic acid, 70% (BerolNobel).

9. Synperonic™ NP-10: Nonylphenol ethoxylated with 10 oxyethylene units(ICI).

10. Tween™ 20: Sorbitanmonolaurate ethoxylated with 20 oxyethylene units(ICI).

11. Plantaren™ 225: C₈₋₁₀ -fatty alcohol glycoside, 70% (Henkel).

12. Plantaren™ 600 CS UP: C₁₂₋₁₄ -alkylpolyglycoside, 50 (Henkel).

13. Berol™ 02: Nonylphenol ethoxylated with 6 oxyethylene units (BerolNobel).

14. Berol™ 922: Coethoxylated/-propoxylated alkylphenol (Berol Nobel).

15. Pleuriol™ PE 6400: Copolymer of ethylene oxide (40%) and propyleneoxide (60%) (BASF).

16. Tween™ 85: Sorbitantrioleate ethoxylated with 20 oxyethylene units(ICI).

17. Arkopon™ T hochkonc: Oleic acid methyltaurid, Na-salt 64% (Hoechst).

18. Berol™ 987: Polyphenyl ether sulphate (Berol Nobel).

19. Surfadon™ LP 300: N-alkylpyrrolidon (GAF).

20. Aerosil™ 972: Synthetic silicic acid (Degussa).

21. Berol™ OX 45-11: C₁₄₋₁₅ -alkylalcohol ethoxylated with 11oxyethylene units (Berol Nobel).

22. Marlipal™ 1618/25: Stearylalcohol ethoxylated with 25 oxyethyleneunits (Huls).

23. Radiasurf™ 7417: Stearic acid esterified with polyethylene glycolwith a molecular weight of 1500 (Oleofina).

24. Berol™ 533: C11-alkylalcohol ethoxylated with 3 oxyethylene units(Berol Nobel).

25. Hydropar 19: Paraffinic mineral oil, 19 mPa x s ved 40° C. (NorskHydro).

26. Radia 7131: 2-ethylhexylstearate, tecn. (Oleofina).

27. PEG E 200: Polyethylene glycol with a molecular weight of app. 200.

28. Moussex 904 SE: 30% silicone emulsion (Protex).

29. Genamin™ S 25: Stearyl amine ethoxylated with 25 oxyethylene units(Hoechst).

30. Genapol OX-130: C₁₂₋₁₅ -alkylalcohol ethoxylated with 13 oxyethyleneunits (Hoechst).

We claim:
 1. A herbicide suspension composition comprising 5-58% byweight of at least one herbicide, said herbicide being suspended in aliquid, aqueous phase and comprising at least one amino group, at leastone carboxylic acid group and at least one phosphor containing acidgroup; and an electrolyte, which is not a surfactant, wherein theelectrolyte is dissolved in the liquid, aqueous phase in an amountcorresponding to at least 5% by weight of the total herbicidecomposition and said composition is surfactant-free.
 2. The herbicidecomposition according to claim 1, wherein the water content is not morethan 65%.
 3. The herbicide composition according to claim 1, wherein theliquid, aqueous phase is continuous as regards water, contains watermiscible organic solvents and the water content is at least 52% byweight of the total amount of solvent in the liquid phase.
 4. Theherbicide composition according to claim 3, wherein the water content isat least 60%.
 5. The herbicide composition according to claim 1, whereinthe herbicide is glyphosate (N-(phosphonomethyl)glycin), glufosinate(4-(hydroxy(methyl)phosphinoyl)-DL-homoalanin,bilanafos(4-hydroxy(methyl)-phosphinoyl)-L-homoalanyl-L-alanyl-L-alanin)and/or glyphosine (N,N-bis(phosphonomethyl)-glycin).
 6. The herbicidecomposition according to claim 1, wherein the herbicide is in its free,non-neutralized form, or is completely or partly converted into its acidor base neutralized salt.
 7. The herbicide composition according toclaim 1, wherein the herbicide is glyphosate, glufosinate, bilanafosand/or glyphosine in its free, non-neutralized form or completely orpartly converted into its respective ammonium salt by reaction withammonia.
 8. The herbicide composition according to claim 1, wherein theamount of herbicide is 10-51%.
 9. The herbicide composition according toclaim 1, wherein the electrolyte is selected from among ammonium salts.10. The herbicide composition according to claim 1, wherein theelectrolyte is selected from the group consisting of sulphates,chlorides, phosphates, phosphites, nitrates, nitrites, rhodanides,sulfamates, sulfites, dithionites and thiosulphates.
 11. The herbicidecomposition according to claim 1, wherein the amount of dissolvedelectrolyte is 5-60% by weight.
 12. The herbicide composition accordingto claim 1, further comprising at least one viscosity regulatingcompound having a maximum particle size of 5 μm, selected from the groupconsisting of naturally occurring and synthetic clays and silicates. 13.The herbicide composition according to claim 12, wherein the amount ofviscosity regulating compounds is 0.1-18%.
 14. The herbicide compositionof claim 12, wherein the naturally occurring and synthetic clays andsilicates are selected from the group consisting of naturally occurringsilicium dioxides; calcium and magnesium silicates, magnesium aluminumsilicates and aluminum silicates.
 15. A process for producing aherbicide suspension composition according to claim 1, comprising thefollowing steps:(a) producing a concentrated herbicide solutioncomprising a herbicide in the form of a salt and water; (b) adding tosaid concentrated herbicide solution an acid or a base thereby resultingin precipitation of the herbicide in its completely or partly free acidform and formation of an electrolyte solution, which solution comprisesthe salt initially formed with the herbicide and the acid or base added.16. A herbicide suspension composition obtainable by the process ofclaim 15.